Transformation of haematite and Al-poor goethite to Al-rich goethite and associated yellowing in a ferralitic clay soil profile of the middle Amazon Basin (Manaus, Brazil)

The red and yellow colours of ferralitic soils in the tropics have for long intrigued pedologists. We have investigated the upward yellowing in a 10-m thick profile representative of the Ferralsols of the plateaux of the Manaus region of Brazil. We determined changes in the nature and crystal chemistry of their Fe oxides by optical and Mössbauer spectroscopy as well as Rietveld refinement of X-ray diffraction patterns. We attribute the upward yellowing of the soil to a progressive transformation of the Fe oxides at nearly invariant iron contents. Aluminium in contrast is strongly mobilized in the uppermost clay-depleted topsoil where there is preferential dissolution of kaolinite and crystallization of gibbsite. Haematite decreases from 35 to 10% of the Fe oxides from the bottom to the top of the profile and the particles become smaller (75–10 nm). Its Al for Fe-substitution remains almost unchanged (10–15 mol %). The average Al-substitution rate of goethite increases from 25 to 33 mol %, and its mean crystal diameter remains in the range 20–40 nm. The proportion of Al-rich goethite (33 mol %) increases at the expense of less Al-substituted Fe oxides (haematite and goethite). This conversion with restricted transfer of iron means that the amount of Al stored in Fe oxides gradually increases. Kaolinite, haematite and Al-poor goethite are thus witnesses of earlier stages of ferralitization of the soil. In contrast, Al-rich goethite and gibbsite initiate the alitization (or bauxitization) of the soil. They correspond to the last generation of soil minerals, which most likely reflects the present-day weathering conditions. The progressive replacement of kaolinite, haematite and Al-poor goethite by new generations of Al-rich goethite and gibbsite attests to greater activities of water and aluminium and smaller activity of aqueous silica in the topsoil than in the subsoil. We interpret this as a consequence of longer periods of wetting in the topsoil that could result from soil aging, more humid climate or both.     

TIME-DEPENDENT SORPTION OF PHOSPHATE BY SOILS AND HYDROUS FERRIC OXIDES

The sorption of inorganic phosphate (P) by soils and hydrous ferric oxides was studied at times up to 192h. An initially rapid decrease in solution P concentration was followed by a much slower decrease between 48 and 192h with soils, Fe gel. and natural goethite, whereas synthetic goethite gave a well-defined equilibrium condition after only 48h. Resolution of the sorption isotherms showed that the increase in P sorption with time involved an appreciable shift of P from a more-physically sorbed form to a chemisorbed form. This was supported by chemical fractionation which showed that NaOH-extractable P was fairly constant with increasing sorption time, whereas the additional sorbed P was extracted by citrate-dithionite-bicarbonate from soils, and by HC1 from Fe gel and natural goethite. These sorbents contained short-range (amorphous) material, whereas synthetic goethite, from which all sorbed P was NaOH –extractable. did not. It is proposed that the time-dependent sorption of P and the associated shift of P to chemisorbed forms, involves the diffusion of P into “structurally porous”, short-range order material.     

Assessing the fixation and availability of sorbed phosphate in soil using an isotopic exchange method

An isotopic exchange method was used to characterize quantitatively the fixation and plant availability of phosphate previously sorbed by soils. In general, the exchangeability of the sorbed phosphate was much higher than its desorbability for both soils and clay minerals. Isotopic exchangeability of the sorbed phosphate increased with sorption saturation during the initial stage (15–60% saturation), but the increase was less with increasing saturation from 60–90% for all soils tested. Therefore a sorption saturation of 60% was recommended as the upper limit of P fertilization in terms of economical efficiency. For clay minerals, with increasing sorption saturation, the isotopic exchangeability of the sorbed P increased significantly for kaolinite and sesquioxides, but decreased for montmorillonite. Most of the phosphate sorbed by montmorillonite and kaolinite was found to be isotopically exchangeable, but only a small amount of the P sorbed by goethite could be exchanged. The P sorbed by Al oxide exhibited isotopic exchangeability between that of kaolinite and Fe oxide. The isotopically exchangeable phosphate pool could readily account for the P uptake of plants and the available P determined by some commonly used chemical methods, such as Olsen-P and Bray-P.     

Sorption of chlorpyrifos to selected minerals and the effect of humic acid

Sorption of chlorpyrifos (CPF) from 2.85 microM (1 mg/L) aqueous solutions in 0.01 M NaCl to montmorillonite, kaolinite, and gibbsite was investigated at 25 degrees C. Uptake of CPF by kaolinite and gibbsite was generally <10%, with pH having at most a small effect. Sorption to montmorillonite was significantly greater, with approximately 50% of the initial CPF being removed from solution below pH 5. Above pH 5 the sorption decreased to about 30%. About 70% of CPF was sorbed to kaolinite and gibbsite after 30 min, whereas on montmorillonite only 50% sorbed in an initial rapid uptake (approximately 30 min) followed by slower sorption, with a maximum achieved by 24 h. Although CPF desorbed completely from kaolinite in methanol, only about two-thirds was desorbed from montmorillonite. CPF has only a weak affinity for the surfaces of kaolinite and gibbsite. In the case of montmorillonite, sorption is significantly stronger and may involve a combination of sorption to external surfaces and diffusion into microporous regions. At pH >6 increased negative surface charge results in a lower affinity of CPF for the external surface. In the presence of 50 mg/L humic acid (HA) the amount of CPF sorbed on gibbsite and kaolinite was 3-4 times greater than that in the binary systems. The HA forms an organic coating on the mineral surface, providing a more hydrophobic environment, leading to enhanced CPF uptake. The HA coating on montmorillonite may reduce access of CPF to microporous regions, with CPF tending to accumulate within the HA coating.     

Iron oxides in lateritic soils from Western Australia

Lateritic soils developed from dolerite contained larger amounts of goethite and haematite than those developed from granite. The goethite/(goethite + haematite) ratio in granitic soils ranged from 0.55 to 1 and from 0.29 to 0.83 in doleritic soils. Maghemite ranged in abundance from 0 to 10% and it only occurred in duricrust. Mole % Al substitution ranged from 16 to 33% in goethite and from 2.5 to 10% in haematite and was similar for both granitic and doleritic soils. Al substitution in maghemite was <5%. A significant, positive correlation (P<0.01) occurred between Al substitution in goethite and the amount of gibbsite in the soil. The dehydroxylation temperature of goethite ranged from 292 to 334°C and was positively correlated with the mole % Al substitution. Goethite crystals varied in size from 16 to 26 nm and haematite crystals from 18 to 59 nm. Goethite and haematite crystals occurred as aggregates of subrounded platy crystals.
Iron oxides obtained by NaOH treatment contained much of the minor element contents of the soils; mean concentrations (μg g⁻¹) were: Zn 19.9, Cu 31, Mn 68, Ni 140, Co 32, Cr 394 and V 696. These minor elements were most abundant in iron oxides derived from dolerite, but were not preferentially associated with goethite or haematite.     

Factors affecting phosphate sorption along a Mediterranean, dolomitic soil and vegetation chronosequence

Phosphate sorption by calcareous soils has been studied mainly on heavily fertilized agricultural soils and soils with calcite as the main carbonate mineral. We examined factors affecting phosphate adsorption in the soils of a semi-arid, mediterranean, dolomitic, soil and vegetation chrono-sequence in southeastern Spain. The youngest soils are highly eroded, Sandy Regosols (Typic Xerorthents) under gorse-scrubland vegetation. These have small P sorption capacities, large Mg-Ca carbonate contents but small amounts of Fe and Al oxides. Small total P (HNO₃/HClO₄ digestion) concentrations (30–130 μg P g^?1), of which up to 90% is Ca-bound (HCl-extractable), are typical of these young soils. P sorption markedly increased when Ca²⁺ was added to the solution. The fractionation of previously sorbed P indicates that the fate of most of this extra-sorbed P is the labile-P fraction sorbed on to (carbonate) surfaces and the apatite-like fraction (NaHCO₃-extractable and HCl-extractable fractions). At the other extreme, older more-intensively weathered, sandy-clay-loam rendzinas (Entic Haploxerolls), supporting dense mature garrigue, have a much greater P adsorption capacity and larger clay and Fe and Al oxide concentrations. They have more total P (ca 400 μg P g^?1), much of it in occluded form (residual fraction). These soils show no significant differences in P sorption whether or not CaCl₂ was used as a background electrolyte. Considering the overall variations within the chronosequence, dithionite extractable Fe and Al are the properties best correlated with P sorption. This support the general finding that crystalline Fe-oxides (e.g. goethite and haematite) appear to be the most important P-sorbing component for soils in the Mediterranean region, rather than amorphous Fe-oxides (e.g. ferrihydrite) as is reported for more mesic areas. Stepwise multiple regression and fractionation data, however, suggest that, provided the soil solution is rich in Ca²⁺, carbonate may also be a significant contributing factor to P sorption, especially in the youngest of these dolomitic soils.     

有机阴离子对磷酸根吸附的影响

在中性条件下,低浓度的柠檬酸、草酸、酒石酸和胡敏酸阴离子都能显著降低针铁矿、非晶氧化铝、高岭石和红壤对磷酸根的吸附,尤其在低磷吸附饱和度下效果更好。有机阴离子抑制磷酸根吸附的能力因有机酸的种类和性质、以及固相的表面特性而异。有机阴离子存在下吸附的磷酸根具有较高的同位素³²P交换活性和解吸率。测定了吸附平衡溶液中铁和铝的浓度。结果表明,在实验条件下(pH 7.0),即使较高浓度的有机酸根(10^-2mol)也只能溶解极少量的铁和铝。有机阴离子络溶作用不足以说明固相吸附磷能力的显著下降。可见,有机阴离子降低磷酸根吸附的机制主要是竞争专性吸附。有机阴离子占据了一部分高亲和力的吸附位,从而降低了土壤固相吸附磷的量,增加了吸附态磷的活性。     

Retention of cobalt by an oxisol in relation to the content of iron and manganese oxides

Abstract

The study aims at determining the cobalt retention properties of various soil components. Therefore, cobalt (Co) sorptions and extractions were carried out using an Oxisol sample before (untreated) and after successive removal of organic matter and active manganese (Mn) oxides (H₂O₂‐treated) and iron (Fe) oxides (H₂O₂+CBD‐treated). A synthetic goethite was included for comparison. Sorption of the four sorbents was determined over a range of Co concentrations (initially 10^‐8 M to 10^‐4 M), pH values (3 to 8) and reaction times (2 hours to 504 hours). The Co species sorbed was Co(ll), since oxygen exclusion during sorption had no effect on the amount sorbed. The pH‐dependent sorption curve (sorption edge) was shifted to lower pH at decreasing initial Co concentration and increasing reaction time. The displacements, in particular of the sorption edges corresponding to the lowest initial Co concentrations, to successively higher pH following removal of Mn oxides, organic matter and Fe oxides could be attributed to sorption onto sites of decreasing Co affinity [Mn oxides (and organic matter) > Fe oxides > kaolinite]. Extractions of sorbed Co at pH 5.5–7.5 with 2 M HCI showed that the extractability decreased with increasing sorption time and decreasing initial Co concentration. The untreated and H₂O₂‐treated soil samples retained sorbed Co at least as firmly as the synthetic goethite, whereas the H₂O₂+CBD‐treated sample (kaolinite) was clearly less effective. The results emphasized the importance of the soil Mn and Fe oxides for Co retention in soils but also the necessity of taken interior sorption sites into consideration.     

高梯度磁场分离后土壤矿物组成的变化

The changes of clay mineral association after high-gradient magnetic separation(HGMS) treatment,and the effects of chemical and physical technologies on concentrating Fe oxides for mian soils in central and southern China were investigated by means of X-ray diffraction (XRD) and chemical analysis methods.Results indicated that the concentrating times of Fe oxides by HGMS treatment were the largest for 0.2-2μm size fraction in the examined soils .For the soils in which 2:1 phyllosilicates were dominant,concentrating times of iron oxides by HGMS treatment were larger than by 5 mol L^-1 NaOH treatment .Phyllosili-cates were decreased after HGMS treatment ;however,the decrease was less than that of kaolinite,The goethite/(goethite hematite) values in Fe oxides of the soils kept virtually constant after HGMS treatment.     

Highly weathered soils in the east coast hinterland of Southern Africa with thick, humus-rich A1 horizons

Strongly weathered red and yellow soils with thick (490–900 mm) humic Al horizons (Haplohumox and Palchumults) derived from sandstones and basic igneous rocks, and occurring near the east coast of Southern Africa, are described and discussed in terms of their distribution, morphology, texture, mineralogy, chemistry, genesis and classification. The high organic matter content (2–5%C) of the Al contributes significantly to a high pH-dependent negative charge, probably to poorer crystallinity of goethite and kaolinite and to the transformation of haematite to goethite. Varying proportions of kaolinite and gibbsite reflect different soil ages within these old landscapes. The yellow colour of aluminous goethite, the main pedogenic iron oxide, is masked in the Al by organic matter and in red B2 horizons by haematite. Temperature may have influenced the broad pattern of occurrence of red and yellow B2 horizons. These soils need not, as previously suggested, have developed from the weathering products of an ancient laterite. Neither Soil Taxonomy nor the South African soil classification system accommodates the soils entirely satisfactorily and possible improvements to the latter are discussed.     

Inhibition of phosphorus sorption to goethite, gibbsite, and kaolin by fresh and decomposed organic matter

The direct effects of dissolved organic matter (DOM) on the sorption of orthophosphate onto gibbsite, goethite, and kaolin were examined using a one-point phosphorus sorption index and the linear Tempkin isotherm model. DOM extracted from fresh and decomposed agricultural residues, as well as model organic and humic acids, were used. Changes in the chemical and sorptive characteristics of the DOM in the absence and presence of added orthophosphate (50 mg l⁻¹) were also determined. For residue-derived materials, DOM sorption to all minerals correlated well with percent hydrophobicity, apparent molecular weight, and phenolic acidity in the absence of added orthophosphate. Sorption of DOM to goethite and gibbsite was significantly decreased in the presence of added P. The correlation coefficient values of percent hydrophobicity, apparent molecular weight, and phenolic acidity to sorption also declined in the presence of added P. Thus, the addition of P substantially lowered fractionation of DOM after sorption to goethite and gibbsite. In contrast, few significant P sorption-induced differences were observed in the kaolin system. According to one-point P sorption results, DOM in the form of Aldrich humic acid, oxalate, and decomposed clover and corn residue, significantly inhibited P sorption to goethite at concentrations of 50 and 200 mg total soluble carbon (C_TS l⁻¹). Phosphorus sorption to gibbsite was significantly inhibited by 50 mg C_TS l⁻¹ derived from decomposed corn residue, fresh dairy manure residue, and oxalate solution. At 200 mg C_TS l⁻¹, all DOM solutions were found to inhibit P sorption to gibbsite. This study suggests that DOM inhibition of P sorption depends on the chemical properties of both the sorbent and the DOM itself. In general, DOM from decomposed organic materials inhibited P sorption to a greater extent than did DOM derived from fresh materials. This stronger inhibition highlights the importance of microbial processes in the release of soluble soil P, a key determinant of P availability to plants.     

Iron-bearing phases in a peat-derived duricrust from Brazil

The formation of aluminium‐substituted iron‐minerals is still subject to debate. We report a case study in a Humic Gleysol soil profile, developed on a sedimentary saprolite, from a basin floor on the Uberaba Plateau (Minas Gerais State, Brazil) where iron‐phases are crystallized by a ferruginization process. The mineralogical and chemical properties were investigated by X‐ray diffraction, thermogravimetric analysis, differential scanning calorimetry and Mössbauer spectroscopy. The specific surface area (BET method) and cation exchange capacity (CEC) were also determined. The soil profile is mainly composed of gibbsite, kaolinite and amorphous alumino‐silicate phases, the latter being more frequent in the H horizon where the organic carbon content is greater. The surface area and CEC values are also greater in the H horizon (58.6 m²g⁻¹ and 4.65 mol_ckg⁻¹, respectively) which indicates an increase in porosity caused by the presence of 20.8% of organic matter and amorphous materials. Goethite occurs as a secondary mineral in the H horizon and as the main mineral in the duricrust in association with haematite. The omnipresence of aluminium in the environment (24.6–46.2% of Al₂O₃) resulted in Al‐substitution in all iron‐bearing phases but the goethite from the H horizon has the greatest Al‐for‐Fe substitution, with at least 20 mole per cent of aluminium. In spite of the greater microporosity and wetness of the H horizon, the immediate contact with the richest Al‐source (gibbsite) favours the precipitation of unusually greatly Al‐substituted goethite instead of haematite in this horizon.     

Development and evaluation of a kinetic model to describe phosphate sorption by hydrous ferric oxide gel

Isotherms for the sorption of inorganic phosphate (P) by hydrous ferric oxide gel (Fe gel) were described by a three-equation Langmuir sorption model. Each equation described sorption within a distinct concentration range or region (I, II, and III) of the overall isotherm. Regions I and II involved chemisorption, whereas region III involved a more physical sorption type. With increasing sorption time between 0.7 and 28.7 days, the extent of sorption in region I increased by more than 30%. In contrast, the extent of sorption in regions II and III remained essentially constant. An equation was developed, based on the change in the sorption maximum of region I (b_I) with increasing sorption time, which described the change in solution P concentration with time. The increase in b_I with time, evaluated by the closeness of fit of this relationship to experimental data, was found to depend on two factors: first, the extent to which P was chemisorbed, and this was affected by pH and ionic strength; second, the batch of Fe gel used. For two different levels of P addition, the proportion of sorbed P which remained extractable in 0.1M NaOH, decreased with increasing sorption time. After 30 days only 88% of the sorbed P remained NaOH-extractable. The data obtained indicated that the increasing chemisorption of P with increasing sorption time involves the diffusion of sorbed P into the bulk of the Fe gel particles. This concept is discussed in relation to mechanisms proposed by previous workers to explain the time-dependence of P sorption.     

高岭石,蒙脱石和针铁矿对泥炭腐殖酸的吸附和分离

Sorption of humic acid (HA) on mineral surfaces has a profound interest regarding the fate of hydrophobic organic contaminants (HOCs) and carbon sequestration in soils. The objective of our study is to determine the fractionation behavior of HA upon sorption on mineral surfaces with varying surface properties. HA was coated sequentially on kaolinite (1:1 clay), montmorillonite (2:1 clay), and goethite (iron oxide) for four times. The unadsorbed HA fractions were characterized by elemental analysis, diffuse reflectance infrared Fourier transform spectroscopy (DRIFT), and solid state ¹³C nuclear magnetic resonance spectroscopy (NMR). The mineral-HA complexes were characterized by DRIFT. Polarity index [(N+O)/C] revealed higher polarity of the unadsorbed HA fractions after coating on kaolinite, reflecting that relatively higher polarity fractions of HA remain unadsorbed. Sorption of aliphatic alcohol fraction along with carbohydrate was prominent on kaolinite surface. DRIFT results of the unadsorbed HA fractions indicated more sorption of aliphatic moieties on both kaolinite and montmorillonite. DRIFT results of the unadsorbed HA fractions after sorption on kaolinite and goethite showed the sorption of the proteinaceous fractions of HA. The HA fractions obtained after coating on goethite showed significant sorption of carboxylic moieties. The results mentioned above comply reasonably well with the DRIFT spectra of the mineral-HA complexes. ¹³C NMR results showed higher sorption of anomeric C on kaolinite surface. Higher sorption of paraffinic fraction was observed on montmorillonite. NMR data inferred the sorption of carboxylic moieties on goethite surface. Overall, this study showed that aliphatic moieties of HA preferentially sorbed on kaolinite and montmorillonite, while carboxylic functional groups play a significant role in sorption of HA on goethite. The sorbed fractions of HA may modify the mineral surface properties, and thus, the interaction with organic contaminants.     

Plant availability of phosphorus sorbed to potential wastewater treatment materials

Ecologically engineered wastewater treatment facilities, such as constructed wetlands and infiltration plants, can be further improved in their P retention by using reactive media with a high P-retention capacity. In a sustainable system, the sorbed P should be recycled in agricultural production. The objective of the present study was to determine the plant availability of P sorbed to different P-retention media. The studied media were: crystalline and amorphous blast furnace slag, natural and burned opoka (a bedrock from Poland), limestone, burned lime, soil from a spodic B horizon, and light expanded clay aggregates (LECA). They were soaked in a P solution, rinsed and dried before incorporation into soil. An additional aim was to compare P taken up by barley with amounts chemically extracted for the estimation of plant-available soil P. P sorbed to the crystalline slag was delivered to the barley plants more efficiently than P added in K₂HPO₄ fertiliser. Soil extraction with acid ammonium lactate correlated well with P taken up by barley and indicated that P bound to Ca is more available to plants than P bound to Al and Fe. The Mg content of the used slag may replace Mg fertilisation in certain soils. It was concluded that among the investigated filter materials, crystalline slag was the most suitable sorbent from an agricultural point of view, since it possessed a large P-sorption capacity and the sorbed P was largely plant available. The heavy metal content of sorption materials must be examined carefully before their application to agricultural soils.     

Interaction of phytases with minerals and availability of substrate affect the hydrolysis of inositol phosphates

The stability and activity of phytases in the soil environment may be affected by their sorption on soil particle surfaces and by substrate availability with important consequences for P cycling and nutrient bioavailability. This work evaluated the interaction of phytases with goethite, haematite, kaolinite, montmorillonite and two oxisol clays and investigated how this interaction is affected when myo-inositol hexakisphosphate (InsP₆) was sorbed on the mineral surfaces. phyA histidine acid phosphatases of fungal origin were used and their ability to release orthophosphate from the InsP₆-saturated minerals was evaluated.The phytases showed a high affinity for the mineral surfaces, with a loss of enzyme activity generally being observed over 24 h (up to 95% of the initially added activity). The loss of phytase activity was dependent on the type of mineral, with kaolinite and montmorillonite showing the greatest effect. Retention of enzyme activity was higher with the two oxisol clays, suggesting that the heterogeneous nature of clay surfaces and the presence of endogenous organic matter may limit the inhibition caused by interaction with minerals.In the presence of mineral surfaces saturated with InsP₆, the partitioning of enzyme activity between the solution and the solid phase was shifted more towards the solution phase, presumably due to the mineral surfaces being occupied by the substrate. However, phytases were not able to release any orthophosphate directly from InsP₆-saturated goethite and haematite, and hydrolysed InsP₆ that was desorbed from haematite. Conversely, in the case of kaolinite and of the oxisol clays, where desorption was limited, phytases appeared to be able to hydrolyse a small fraction of the InsP₆ adsorbed on the surfaces. These findings suggest that the bioavailability of P from inositol phosphates is governed to a large extent by the mineral composition of soil and by competitive effects for sorption on reactive surfaces among inositol phosphates and phytases.     

Phosphate fertilizer compounds in soils: Their influence on the relationship between plant yield and soil test value

Abstract

A pot experiment with a lateritic soil measured the relative effectiveness of monocalcium phosphate (MCP) fertilizers and six phosphate (P) compounds which were used to represent fertilizer compounds that may be present in soils. The P compounds were added at various rates, wheat was grown, and the treated soils were extracted with eight standard soil P‐test reagents. The relative effectiveness (RE) values for the fertilizer compounds based on plant yield were 1.00, 0.33, 0.32, 0.20, 0.16, 0.15, and 0.09 for MCP, P sorbed on gibbsite (Gi‐P), P sorbed on goethite (Go‐P), P sorbed on calcite (Ca‐P), AlPO₄ (Al‐P), Apatite (Ap‐P) and FePO₄ (Fe‐P), respectively. For soil treated with Ap‐P, Gi‐P, Go‐P, Ca‐P, and MCP, soil test values were significantly related to the yield of wheat. Only Bray 1, Bray 2, ammonium oxalate, and Colwell soil tests adequately predicted yield for Al‐P treated soil, and no soil test was suitable for soil treated with Fe‐P. Where soil tests were predictive of yield, separate calibrations were required for the different P compounds. For example, in order to obtain 100 mg of wheat per pot from soil that was treated with Al‐P, Fe‐P, Ap‐P, Gi‐P, Go‐P, Ca‐P, and Bray 2 soil test values of 122, 8, 387, 112, 9, 202, and 50 ug/g, respectively, were required.     

Sorption of 2,4-D and other phenoxy herbicides to soil, organic matter, and minerals

Purpose

We review 2,4-dichlorophenoxyacetic acid (2,4-D) and other phenoxy herbicide sorption experiments.

Methods

A database with 469 soil–water distribution coefficients K _d (in liters per kilogram) was compiled: 271 coefficients are for the phenoxy herbicide 2,4-D, 9 for 4-(2,4-dichlorophenoxy)butyric acid, 18 for 2-(2,4-dichlorophenoxy)propanoic acid, 109 for 2-methyl-4-chlorophenoxyacetic acid, 5 for 4-(4-chloro-2-methylphenoxy)butanoic acid, and 57 for 2-(4-chloro-2-methylphenoxy)propanoic acid. The following parameters characterizing the soils, solutions, or experimental procedures used in the studies were also compiled if available: solution CaCl₂ concentration, pH, pre-equilibration time, temperature, soil organic carbon content (f _oc), percent sand, silt and clay, oxalate extractable aluminum, oxalate extractable iron (Oxalate Fe), dithionite–citrate–bicarbonate extractable aluminum, dithionite–citrate–bicarbonate extractable iron (DCB Fe), point of zero negative charge, anion exchange capacity, cation exchange capacity, soil type, soil horizon or depth of sampling, and geographic location. K _d data were also compiled characterizing phenoxy herbicide sorption to the following well-defined sorbent materials: quartz, calcite, α-alumina, kaolinite, ferrihydrite, goethite, lepidocrocite, soil humic acid, Fluka humic acid, and Pahokee peat.

Results

The data review suggests that sorption of 2,4-D can be rationalized based on the soil parameters pH, f _oc, Oxalate Fe, and DCB Fe in combination with sorption coefficients measured independently for humic acids and ferrihydrite, and goethite.

Conclusions

Soil organic matter and iron oxides appear to be the most relevant sorbents for phenoxy herbicides. Unfortunately, few authors report Oxalate Fe and DCB Fe data.     

The influence of aminopolycarboxylates on the sorption of copper (II) cations by (Hydro)oxides of iron,Aluminum, and manganese

The influence of some complexing agents of (poly)aminopolycarboxylic acids (diethylenetriaminopentaacetic acid (DTPA), ethylenediaminotetraacetic acid (EDTA), nitrilotriacetic acid (NTA), and iminodiacetic acid (IDA)) on the sorption of Cu²⁺ by crystal and amorphous (hydr)oxides of Fe(III), Al(III), and Mn(IV) that are widespread mineral components of soils was studied. The obtained results are considered in terms of complex-formation in the solution and on the sorbent’s surface. The effect of the complexing agents on the metal sorption (mobilization/immobilization) is determined by (1) the stability, structure, and sorption capability of compexonates formed in the solution; (2) the acidity, and (3) the nature of the sorbent. The desorption effect on Cu²⁺ cations was found to change in the following sequence of complexing agents: EDTA > DTPA ? NTA > IDA. The high-dentate complexing agents (EDTA, DTPA) had the greatest impact on ?u²⁺ cations bound with crystalline (hydr)oxides of Fe, Al, and Mn. The low denticity of the complexing agents (IDA, NTA) and binding of ?u²⁺ with amorphous sorbents leads to the weakening of desorption. The decrease in acidity promoted the mobilization of the metal under the influence of complexing agents; the increase in acidity caused its immobilization. The growth in the mobility of heavy metals bound with soil (hydr)oxides of Fe, Al, and Mn due to the complexing agents entering the surface and ground water is considered a factor of ecological risk.     

Use of the Kubelka—Munk theory to study the influence of iron oxides on soil colour

The Kubelka–Munk theory, which is commonly applied to ‘pigment mixtures’, adequately predicted the colour of mixtures of synthetic haematite, synthetic goethite and deferrated soil powders. The theory illustrated the higher pigmenting effect of haematite compared with goethite. In mixtures containing haematite the calculated colour coordinates could be combined into simple ‘redness’ indices that were highly correlated with haematite content and were not appreciably influenced by goethite. The theory was also applied to the study of the chromatic characteristics of 98 soils, differing widely in their origin but having an organic matter content <2% in which haematite or goethite was the dominant Fe oxide. The theory showed that the average ‘soil’ haematite and ‘soil’ goethite had colours similar to those of their synthetic counter-parts, whereas the rest of the soil components could be considered as an essentially ‘grey’ matrix. It was also useful in predicting the haematite and goethite contents of soils either from several reflectance measurements of soil-white standard mixtures or from the indices of redness developed for the synthetic mixtures.