Investigating the role of mineral-bound humic acid in phenanthrene sorption

Contaminant-soil interaction studies have indicated that physical conformation of organic matter atthe solid-aqueous interface is important in governing hydrophobic organic compound (HOC) sorption. To testthis, organo-clay complexes were constructed by coating montmorillonite and kaolinite with peat humic acid (PHA) in Na+ or Ca2+ dominated solutions with varying pH and ionic strength values. The solution conditions encouraged the dissolved PHA to adopt a "coiled" or "stretched" conformation prior to interacting with the clay mineral surface. Both kaolinite and montmorillonite organo-clay complexes exhibited higher phenanthrene sorption (Koc values) with decreasing pH, indicating that the coiled configuration provided more favorable sorption conditions. Evidence from 1H high-resolution magic angle spinning (HR-MAS) nuclear magnetic resonance (NMR) indicated that polymethylene groups were prevalent at the surface of the organo-clay complexes and may enhance sorptive interactions. Preferential sorption of polymethylene groups on kaolinite and aromatic compounds on montmorillonite may also contribute to the difference in phenanthrene sorption by PHA associated with these two types of clay. This study demonstrates the importance of solution conditions in the sorption of nonionic, hydrophobic organic contaminants and also provides evidence for the indirect role of clay minerals in sorption of contaminants at the soil-water interface.     

Clay minerals affect the stability of surfactant-facilitated carbon nanotube suspensions

Carbon nanotubes (CNTs), because of their wide application, will inevitably enter aquatic systems, but the fate and transport of their suspensions in the environment are largely unknown. Clay minerals are expected to interact with CNT suspensions, affecting their fate and bioavailability. This study investigated the influence of clay minerals (kaolinite and montmorillonite) on the stability of surfactant (SDBS, CTAB, and TX100) facilitated multiwalled CNT (MWCNT) suspensions. Adsorption of the surfactants by MWCNTs and clay minerals was also examined. This is a first study on the interaction between clay minerals and surfactant-CNT suspensions. Sorption of SDBS by clay minerals and MWCNTs followed the order MWCNTs > montmorillonite approximately kaolinite; but sorption of CTAB and TX100 followed the order montmorillonite > MWCNTs > kaolinite. For SDBS suspended MWCNTs, introduction of montmorillonite and kaolinite could not change their stability; for CTAB suspended MWCNTs, both montmorillonite and kaolinite greatly deposited the suspended MWCNTs; for TX100 suspended MWCNTs, montmorillonite could partially deposit the suspended MWCNTs, whereas kaolinite showed minimal effect. Two mechanisms of clay minerals affecting MWCNT suspensions are (1) removal of surfactants by clay minerals from solution and MWCNT surface and (2) bridging between clay mineral and MWCNTs by surfactant.     

无机矿物黏土吸附性能的改进及其机理研究

对无机膨润土进行了聚胺改性,得到有机复合膨润土。通过X-射线等手段对试样进行了表征分析。经过有机改性后,膨润土亲水性降低,松香酸能够被有机膨润土吸附而进入其间层。复合有机胺之后,膨润土内外表面憎水性提高,增强了对憎水性物质松香酸的吸附力。与无机膨润土相比,有机复合膨润土对松香酸的吸附量提高,吸附速率加快。     

Adsorption of the herbicide simazine by montmorillonite modified with natural organic cations

Three organic cations with a natural origin (L-carnitine, L-cystine dimethyl ester, and thiamine) were introduced at different loadings in the interlayer of a low-charge montmorillonite, and the performance of the modified clays as adsorbents of the herbicide simazine was investigated using batch adsorption-desorption experiments. The organic cations were selected on the basis of their natural origin and the presence of diverse functional groups in their structures, which was expected to influence simazine adsorption. Elemental analysis and spectroscopy results demonstrated the presence of the organic cations in the modified montmorillonites and their entrance in the clay mineral interlayers. Batch adsorption results showed that modification with thiamine (K(f) = 96-138), cystine dimethyl ester (K(f) = 400-753), and especially carnitine (K(f) > 10 000) enhanced the adsorption of simazine by montmorillonite (K(f) = 28-47). It appeared that the specific interlayer microenvironment provided by the functional groups of each organic cation was an important factor controlling the adsorption efficiency of the modified clays. For carnitine and cystine dimethyl ester, the increase in simazine adsorption was considerably greater than that observed after montmorillonite modification with "classical" alkylammonium cations, such as phenyltrimethylammonium or hexadecyltrimethylammonium. This illustrated how modification of smectitic clay minerals with natural organic cations containing appropriate functional groups can be a useful strategy to improve the performance of organoclays for the removal of specific organic pollutants from the environment.     

Phosphate solubility tests—interference of some accessory minerals

Solubilities of apatites isolated from random samples of Israeli phosphates were determined in citric acid, formic acid and neutral ammonium citrate. Minerals normally associated with the apatites in rock phosphates were then added and the solubility tests repeated. Calcite markedly reduced the apparent solubility in the three solvents but gypsum interfered only in the case of neutral ammonium citrate. The accepted solubility tests therefore favour phosphates containing inert accessory minerals such as quartz and do not reflect the solubility of apatite when it is associated with calcite. A method based on determining the solubility of apatite instead of rock phosphate is suggested.     

膨润土的有机改性及吸附性能研究

以十六烷基三甲基溴化铵(HTMAB)、自制的低分子质量聚胺及四甲基铵对膨润土进行有机改性,通过红外光谱、X射线检测分析证实,HTMAB可有效地与膨润土进行复合,并以一定角度倾斜于层间。不同有机胺改性膨润土对松香酸吸附性能的研究结果表明,改性膨润土中需复合一定强度的有机相,才能更有效地吸附有机污染物松香酸。     

Interactions of DNA with clay minerals and soil colloidal particles and protection against degradation by DNase

Adsorption, desorption, and degradation by nucleases of DNA on four different colloidal fractions from a Brown soil and clay minerals were studied. The adsorption of DNase I and the structures of native DNA, adsorbed and desorbed, were also investigated by Fourier Transform Infrared (FTIR), circular dichroism (CD), and fluorescence spectroscopy, to determine the protection mechanism of DNA molecules by soil colloids and minerals against enzymatic degradation. Kaolinite exhibited the highest adsorption affinity for DNA among the examined soil colloids and clay minerals. In comparison with organomineral complexes (organic clays), DNA was tightly adsorbed by H2O2-treated clays (inorganic clays). FTIR spectra showed that the binding of DNA on kaolinite and inorganic clays changed its conformation from the B-form to the Z-form, whereas montmorillonite and organic clays retained the original B-form of DNA. A structural change from the B- to the C-form in DNA molecules desorbed from kaolinite was observed by CD spectroscopy and confirmed by fluorescence spectroscopy. The presence of soil colloids and minerals provided protection to DNA against degradation by DNase I. The higher level of protection was found with montmorillonite and organic clays compared to kaolinite and inorganic clays. The protection of DNA against nuclease degradation by soil colloids and minerals is apparently not controlled by the adsorption affinity of DNA molecules for the colloids and the conformational change of bound DNA. The higher stability of DNA seemed to be attributed mainly to the presence of organic matter in the system and the adsorption of nucleases on soil colloids and minerals. The information obtained in this study is of fundamental significance for the understanding of the behavior of extracellular DNA in soil environment.     

Clay particles destabilize engineered nanoparticles in aqueous environments

Given the ubiquity of natural clay minerals, the most likely interaction of nanoparticles released into an aquatic environment will be with suspended clay minerals. Thus, the transport of engineered nanoparticles in the subsurface and the water column will most likely be altered by their interaction with these minerals. We studied the interactions of two of the most produced nanoparticles, Ag and TiO(2), and montmorillonite to determine how heteroaggregation can alter the stability of nanoparticle/clay mineral mixtures. Since at low pH montmorillonite has a negatively charged basal plane and positively charged edges, its interaction with these nanoparticles at different pH lead to unusual behaviors. There are six different interactions for each clay-nanoparticle pair. At pH values below the IEP of montmorillonite edge site, montmorillonite reduced the stability of both negatively charged Ag and positively charged TiO(2) nanoparticles. Surprisingly this enhanced coagulation only occurs within an intermediate ionic strength range. The spillover of the montmorillonite basal plane electric double layer to the montmorillonite edge may screen the electrostatic attraction between Ag and the montmorillonite edge at low ionic strength, whereas a repulsion between TiO(2) and montmorillonite face sites may restabilize the mixture.     

Nitrogen form affects yield and taste of tomatoes

Different nitrogen forms in organic or mineral fertilizers affect yield, quality and taste of tomatoes. Tomato plants were grown in a greenhouse for 10 weeks and fertilized with two different organic fertilizers (manure or grass and clover mulch) or with three different mineral nutrient solutions (NO₃^?:NH₄⁺) ratios 4:1 or 1:4). In an attempt to mimic the nutrient supply of the organic production systems, mineral fertilizers with ammonium as the dominating N‐source were combined with two chloride levels. Total nitrogen supply was 650 mg N plant^?1 week^?1 in all treatments. There was no difference in the yield of red tomatoes between the treatments (mean 1.95 kg FW plant^?1). However, the yield of green tomatoes at the final harvest was significantly higher in the mineral nutrient treatments (mean 1.37 kg FW plant^?1) compared with the organic treatments (mean 0.88 kg FW plant^?1). Plant biomass was higher for the mineral nutrient treatments (mean 1.05 kg FW plant^?1) compared with the organic treatments (0.89 kg and 0.72 kg FW plant^?1 in the manure and the grass and clover mulch treatments, respectively). Significantly higher scores were achieved for sweetness, acidity, flavour and acceptance for the tomatoes grown with the organic or the ammonium‐dominated treatments compared with the tomatoes grown with the nitrate dominated nutrient solution. It is suggested that ammonium is an equivalent nitrogen source for tomato plants compared with nitrate and that, when tomato plants are supplied with reduced nitrogen forms such as ammonium or organic nitrogen, an improved tomato fruit taste can be observed. Copyright © 2005 Society of Chemical Industry     

Lead phosphate minerals: solubility and dissolution by model and natural ligands

Due to their relatively low solubility, lead-phosphate minerals may control Pb solution levels at a low value in natural environments. We reportthe solubility of Pb from two lead-orthophosphate mineral suspensions (beta-Pb9(PO4)6 and PbHPO4) after aging for 3 years. Lead (Pb2+) activity in the aged suspensions was compared to the activity calculated using the Ksp values of various Pb-PO4 minerals reported in the literature. We also determine the time-dependent dissolution of the aged lead-phosphate minerals by organic and inorganic ligands containing S-functional groups (cysteine, methionine, and thiosulfate) and by a soil extracted humic acid. We find the activity of Pb2+ in the aged lead-phosphate suspensions to be 1-2 orders of magnitude higher than predicted by the Ksp values reported in the literature. Disagreement between measured and Ksp-calculated activities has been reported in other investigations of Pb-PO4 minerals; we compiled some of the data and present them together with our results. Furthermore, the time-dependent dissolution experiments indicate that, in most cases, lead phosphates are partly dissolved in the presence of soluble ligands, i.e., model sulfides and humic acid. The soil-extracted humic acid enhanced the dissolution of Pb from the high pH (7.2) lead-phosphate (beta-Pb9(PO4)6) mineral while suppressing Pb dissolution from the low pH (3.8) lead-phosphate (PbHPO4) mineral. While the low molecularweight sulfur-containing ligands enhanced Pb dissolution, their effect was less pronounced. We conclude that (i) nonequilibrium conditions prevail in the mineral suspensions even after 3 years of aging; and (ii) soluble ligands present in soils, sediments, and natural waters can potentially dissolve Pb from lead-phosphate minerals; such ligands, then, may enhance the biological availability and mobility of Pb in the environment.     

Reduction of nitroaromatic compounds by Fe(II) species associated with iron-rich smectites

Reductive transformation reactions involving mineral-bound Fe2+ species are of great relevance for the fate of groundwater contaminants. For clay minerals, which are ubiquitously present in soils and sediments, the factors determining the reactivity of structural Fe2+ and surface-bound Fe2+ are not well understood. We investigated the reactivity and availability of Fe2+ species in suspensions of chemically reduced montmorillonite (SAz-1) as well as in suspensions of oxidized and reduced nontronite (SWa-1, ferruginous smectite) using two acetylnitrobenzene isomers as reactive probe compounds. The analyses of the reduction kinetics of the two nitroaromatic compounds (NACs) suggested that Fe2+ bound in the octahedral layer of reduced smectites is the predominant reductant and that electron transfer presumably occurs via basal siloxane planes. In contrast, reduction of NACs by Fe2+ associated with oxidized nontronite is orders of magnitude slower than reduction by octahedral Fe2+. Reductive transformation and reversible, nonreactive electron donor-acceptor (EDA) complexation of NACs at basal smectite surfaces occur simultaneously at reduced montmorillonite exhibiting low structural iron content. In contrast, EDA complexation was not observed in suspensions of reduced iron-rich nontronite. Due to the similar reduction rate constants measured for the two NACs, we propose that the (re)- generation of octahedral Fe2+ sites, e.g., by electron transfer and/or Fe rearrangement within the octahedral nontronite layers, partly limited the rate of contaminant transformation. Since iron in clay minerals is available for microbial reduction, our study suggests that octahedral Fe2+ can contribute to abiotic contaminant transformation in anoxic environments.     

Fixation of added ammonium and nitrification of fixed ammonium in soil clays

Under wet conditions there was no fixation of added ammonium by soil-clays (< 2μ fraction) extracted from Colombian soils. The extent of average fixation by the clays was approximately in the ratio 1 : 12 : 16, when air-drying, oven-drying (100°), and five cycles of wetting and oven-drying were used. The highest fixation occurred in clays which contained montmorillonite and the lowest in those which contained kaolinite as the main clay minerals. The extent of nitrification of fixed ammonium during incubation under aerobic conditions for 6 weeks ranged from 6% to 88% of the fixed ammonium, and was not related to the main types of clays present.     

The effects of boiling and leaching on the content of potassium and other minerals in potatoes

ABSTRACT:  The white potato ( Solanum tuberosum L.) is a valuable source of potassium in the human diet. While most consumers benefit from high levels of potassium in potato tubers, individuals with compromised kidney function must minimize their potassium intake. This study was undertaken to determine the effects of leaching and boiling on levels of potassium and other minerals in potato tubers. Leaching alone did not significantly reduce levels of potassium or other minerals in tubers. Boiling tuber cubes and shredded tubers decreased potassium levels by 50% and 75%, respectively. Reductions in mineral amounts following boiling were observed for phosphorus, magnesium, sulfur, zinc, manganese, and iron. There was no difference between the leaching and boiling treatment and the boiling treatment. In addition, mineral levels in tubers of 6 North American potato cultivars are reported. Significant differences in mineral levels were detected among cultivars, but they were too small to be nutritionally important. Individuals wishing to maximize the mineral nutrition benefits of consuming potatoes should boil them whole or bake, roast, or microwave them. Those who must reduce potassium uptake should boil small pieces before consuming them.     

Nitrogen fertiliser source effects on the growth and mineral nutrition of pepper (Capsicum annuum L.) and wheat (Triticum aestivum L.)

BACKGROUND: The presence of stable mixed nitrogen forms (such as nitrate/ammonium/urea or nitrate/urea) in the soil solution is due to the use of nitrification and/or urease inhibitors in urea‐based fertilisers. However, there is no specific information in the literature comparing the efficiency of these urea mixed nitrogen forms as a nitrogen source for plants with that of nitrate and ammonium/nitrate. The aim of this study was to compare the effects on plant growth and mineral nutrition of different nitrogen forms, including mixed nitrogen forms containing urea. RESULTS: The results indicated that for both wheat (Triticum aestivum L.) and pepper (Capsicum annuum L.) the growth of plants fed mixed nitrogen forms containing urea was generally similar to that of plants receiving nitrate and nitrate/ammonium. Only in the case of pepper did ammonium/urea nutrition cause a significant decrease in plant growth. The presence of nitrate corrected the negative effects of mixed nitrogen forms containing ammonium and/or urea on the growth of pepper plants. CONCLUSION: Mixed nitrogen forms containing urea did not cause any negative effect on plant growth or mineral nutrition. In fact, plants fed mixed nitrogen forms containing urea had higher shoot concentrations of potassium, phosphorus, iron and boron than plants receiving nitrate. Copyright © 2007 Society of Chemical Industry     

Yield,nitrate levels and sensory properties of spinach as influenced by organic and mineral nitrogen fertiliser levels

Spinach was fertilised at two levels of nitrogen, 140 kg/ha (x) and 420 kg/ha (3x), using split applications of ammonium sulphate and dried blood as nitrogen sources. A single application of ammonium sulphate (x) 19 days prior to harvest was also tested. A no-nitrogen control was also employed. The x rate of mineral nitrogen produced statistically the same yield as the 3x organic source but at a lower tissue nitrate level. The 3x mineral fertiliser produced both the highest yield and nitrate concentration. Excluding late fertiliser application, nitrate levels were closely related to yield and dependent upon rate of nitrogen availability from each of the two sources. Late application of mineral nitrogen did not increase yield over a no-nitrogen application control, but resulted in an eight-fold increase in tissue nitrate. Triangle taste panels demonstrated significant differences in raw, cooked, and frozen samples when comparing the no-nitrogen application against both the 3x organic and mineral nitrogen applications and the late mineral application. No significant sensory differences resulted between organic and mineral fertilisers at either application level. Colour measurements revealed that higher nitrogen application darkened colour. Organic sources gave darker colours than corresponding mineral fertiliser levels. Late application of mineral nitrogen resulted in the darkest colour. Gas–liquid chromatography headspace scans demonstrated that increasing nitrogen rates from x to 3x approximately doubled total peak area. No qualitative differences were noted. Late application of mineral fertiliser resulted in a headspace scan similar to those obtained at the 3x nitrogen rates.     

Efficiency of urease and nitrification inhibitors in reducing ammonia volatilization from diverse nitrogen fertilizers applied to different soil types and wheat straw mulching

BACKGROUND: Some authors suggest that the absence of tillage in agricultural soils might have an influence on the efficiency of nitrogen applied in the soil surface. In this study we investigate the influence of no‐tillage and soil characteristics on the efficiency of a urease inhibitor (N‐(n‐butyl)thiophosphoric triamide, NBPT) and a nitrification inhibitor (diciandiamide, DCD) in decreasing ammonia volatilization from urea and ammonium nitrate (AN), respectively. RESULTS: The results indicate that ammonia volatilization in soils amended with urea was significantly higher than in those fertilized with AN. Likewise, the main soil factors affecting ammonia volatilization from urea are clay and sand soil contents. While clay impedes ammonia volatilization, sand favours it. The presence of organic residues on soil surface (no‐tillage) tends to increase ammonia volatilization from urea, although this fact depended on soil type. The presence of NBPT in urea fertilizer significantly reduced soil ammonia volatilization. This action of NBPT was negatively affected by acid soil pH and favoured by soil clay content. CONCLUSION: The presence of organic residues on soil surface amended with urea increased ammonia volatilization, and was particularly high in sandy compared with clay soils. Application of NBPT reduced ammonia volatilization although its efficiency is reduced in acid soils. Concerning AN fertilization, there were no differences in ammonia volatilization with or without DCD in no‐tillage soils. Copyright © 2011 Society of Chemical Industry     

Removal of mineral oil migrated from paperboard packing during cooking of foods in boiling water

The removal of mineral oil migrated from paperboard into food during cooking in boiling water was investigated: noodles, rice, couscous and chocolate drink were cooked as adequate as well as far beyond normal; samples were analyzed for mineral oil before and after cooking. Since direct extraction of cooked noodles with hexane resulted in low yield, water was first extracted with ethanol. During adequate cooking, removal of mineral oil from rice amounted to about 50%, depending on the type, the duration of cooking, and whether or not an excess of water was applied. From couscous, 43% was evaporated when boiled for an excessively long time, but no significant amount when boiling water was added corresponding to the normal procedure. Cooking of noodles did not significantly reduce the mineral oil content. Removal of the mineral oil from dry food is probably hindered by water entering the pores and acting like a barrier: to reach the boiling water, the hydrocarbons would have to diffuse through this water to the surface of the particle, which is impeded by the low solubility of the hydrocarbons.     

Sorption of the herbicide dichlobenil and the metabolite 2,6-dichlorobenzamide on soils and aquifer sediments

The worldwide used herbicide dichlobenil (2,6-dichlorobenzonitrile) has resulted in widespread presence of its metabolite 2,6-dichlorobenzamide (BAM) in pore- and groundwater. To evaluate the transport of these compounds we studied the sorption of dichlobenil and BAM in 22 sediment samples of clayey till, sand, and limestone including sediments exhibiting varying oxidation states. Dichlobenil sorbed to all investigated sediments, with a high sorption in topsoils (Kd = 7.4-17.4 L kg(-1)) and clayey till sediments (Kd = 2.7-126 L kg(-1)). The sorption of the polar metabolite BAM was much lower than the sorption of dichlobenil but followed the same tendency with the highest sorption in the topsoils (Kd = 0.24-0.66 L kg(-1)) and in the clayey till sediments (Kd = 0.10-0.93 L kg(-1)). The sorption of both compounds was significantly higher (2-47 times) in the unoxidized (reduced) clayey till than in the weathered (oxidized) clayey till. Such a difference in sorption capacity could neither be explained by a higher organic carbon content, sorption to clay minerals, differences in clay mineralogy, nor by blocking of reactive surface sites on clay minerals by iron oxides. However, by removing an average of 81% of the organic carbon from the reduced clayey till with H2O2, the sorption decreased on average 50%. Therefore, most of the sorption capacity in the reduced clayey till was related to organic carbon, which indicates that sorption processes are affected by changes in organic compound composition due to weathering.     

Decomposition of hydrogen peroxide driven by photochemical cycling of iron species in clay

The reactivity of iron-bearing clays to catalyze the decomposition of hydrogen peroxide (H2O2) under light irradiation was investigated. Free iron oxides and structural iron in clay octahedral lattice are contained simultaneously in montmorillonite K10 (MK10), a representative natural clay mineral. By pretreatment of clay with the particular method, the reactivities of the two kinds of iron species were differentiated. It was found that free iron oxides on clay surface efficiently catalyzed the decomposition of H202 under UV light irradiation but structural iron in the octahedral lattice showed poor reactivity. This was found to result from the difference in production of Fe(II) species under UV irradiation between iron oxides and structural iron. When photoreactive substances such as N,N-dimethylaniline (DMA), rhodamine B (RhB), or malachite green (MG) were introduced, structural iron was found to promote greatly the decomposition of H202. The reduction of clay iron(II) to iron(II) is essential for the decomposition of H2O2, which is achieved by light-induced ligand to metal charge transfer (for iron oxides) or organic matters donating electrons upon irradiation (for structural iron). The light-induced redox cycling of iron did not lead to the release of iron and decomposition of H202 primarily localized on the clay surface. This work implies that iron-bearing clays could be a sink of H2O2 in the environmental system.     

Heterogeneous decomposition of CHF2OCH2CF3 and CHF2OCH2C2F5 over various standard aluminosilica clay minerals in air at 313 K

The heterogeneous decomposition of CHF2OCH2C2F5, a potential substitute for hydrofluorocarbons, over aluminosilica clay minerals in air, was confirmed to occur at 313 K in a closed-circulation reactor. HC(O)OCH2C2F5, the gaseous main product was produced through hydrolytic elimination of F atoms from the CHF2OCH2- group. CHF2OCH2CF3 also decomposed to HC(O)OCH2CF3 over the clay minerals. The pseudo-first-order rate constants were determined for the decompositions over eight types of clay minerals (19 samples). The various clay minerals had different abilities to decompose these hydrofluoroethers. The decomposition rates per Brunauer-Emmett-Teller surface area and the conversion ratios to HC(O)OCH2C2F5 or HC(O)OCH2CF3 for the reactions over kaolinite, halloysite, and illite were high in comparison to those for the same reactions over montmorillonite, hectorite, and nontronite. The dependence of this heterogeneous reaction on temperature and relative humidity indicates that, in the environment, the reaction could be important only in hot, dry regions. The results did not suggest that sunlight would directly accelerate the decay of CHF2OCH2CF3 or CHF2OCH2C2F5. In the presence of clay-containing soils in arid areas, this hydrolytic oxidation reaction may significantly affect both the lifetime and the degradation products of CHF2OCH2CF3 and CHF2OCH2C2F5 in the troposphere.