Fate of atrazine and chlorpyrifos during solid state fermentation—examination of processes

Abstract

Solid state fermentation (SSF) was investigated as a means to dispose of two commonly used pesticides, chlorpyrifos (O, O‐diethyl O‐(3,5,6‐trichloro‐2‐pyridyl) phosphorothioate) and atrazine (2‐chloro‐4‐ethylamino‐6‐isopropylamino‐1,3,5‐triazine). SSF experiments were carried out in bench‐scale bioreaetors (equipped with CO₂ and volatile organic traps) containing a mixture of lignocellulosic materials and a radiolabeled pesticide. Ethyl acetate‐extractable, alkali soluble, and alkali insoluble fractions were evaluated for radioactivity following a 60‐d incubation period at 40°C. The majority of the [2, 6‐pyridyl‐¹⁴C]chlorpyrifos was associated with the ethyl acetate extract (about 74%), 17% was trapped as organic volatiles by polyurethane foam traps and < 0.5% of the chlorpyrifos was mineralized to CO². Only small amounts of the radioactivity were associated with alkali soluble (0.0003%) and alkali insoluble (0.3%) fractions. In the [¹⁴C‐U‐ring] atrazine bioreactors, very little of the radioactivity volatilized (<0.5%) and less than 0.5% was mineralized to CO₂. Approximately 57% of the applied radioactivity was associated with the ethyl acetate extract while 9% and 24% of the radioactivity was associated with the alkali soluble (humic and fulvic acids) and alkali insoluble fractions, respectively. Possible reaction mechanisms by which covalent bonds could be formed between atrazine (or metabolites) and humic substances were investigated. The issue of bound atrazine residue (alkali soluble fraction) was at least partially resolved. Oxidative coupling experiments revealed that formation of covalent bond linkages between amino substituent groups of atrazine residue and humic substances is highly unlikely.     

Chlorothalonil binding to aquatic humic substances assessed from gas purge studies

Abstract

Fate of the fungicide chlorothalonil (TCIN) binding to dissolved organic acid fractions was quantified using gas‐purge desorption studies. Binding studies were conducted to measure the dissolved organic carbon partition constant (K_DOC) with aquatic fulvic and humic acid fractions purified from cranberry bog water. Desorption studies at DOC concentrations up to 50 mg L^‐1 resulted in mean log K_DOC values of 4.63 (s.d.=0.5, n=8) and 4.81 (s.d.=0.7, n=7) for fulvic and humic acids, respectively. These values deviated from reported K_OC (organic carbon) values by 0.5 to 1.5 orders of magnitude. The relationship between K_OC and K_DOC did not conform to accepted ratios of 10: 1 to 3: 1, although these studies were conducted with the strong hydrophobic fraction of DOC. Binding was rapid suggesting hydrophobic partitioning or weak Van Der Waals forces as binding mechanisms. The strong binding potential for TCIN to aquatic humic substances corresponds to increased solubility in the aqueous system. Sorption to DOC suggests a possible transport mechanism which may result in elevated concentrations of TCIN in cranberry bog systems.     

Removal of humic substances from water by means of calcium-ion-enriched natural zeolites.

The ability of the natural zeolited Neapolitan Yellow Tuff (NYT) enriched with calcium ions to remove humic acids from water was evaluated by batch adsorption equilibrium tests and dynamic experiments carried out by percolating humic acid solutions through a small NYT column (breakthrough curves). Under the experimental condition explored, the sorption capacity increases with the ionic strength and has the highest value at pH 7.4. The partition coefficient for a low concentration of humic acid ([humic acid] --> 0), at pH 7.4 in 0.01 M sodium chloride, was approximately 1000 L/kg, versus the value of approximately 100 L/kg in the absence of the alkaline metal salt. Therefore, after humic acids have been adsorbed in a column filled with the calcium-ion-enriched tuff, a reduction of the salt concentration in the ongoing solution enhances the release of the adsorbed material. These findings show that NYT can be used for the removal of humic acids from water.     

毒死蜱在不同土壤腐殖酸上的吸附/解吸特征

通过平衡振荡法研究毒死蜱在不同来源土壤腐殖酸(Has)上的吸附/解吸行为.结果表明,毒死蜱在Has上的等温吸附行为用Freundlich模型描述相对更合理;它们的吸附等温线在实验范围内基本呈直线,且吸附能力很强,顺序为:紫色潮土Has＞黄壤Has＞中性紫色土Has＞酸性紫色土Has＞腐殖土Has;但毒死蜱的解吸率较小,其值均小于26.70%,有明显的滞后现象,尤其是腐殖土Has和紫色潮土Has,固定能力顺序为:紫色潮土Has＞腐殖土Has＞中性紫色土Has＞酸性紫色土Has＞黄壤Has.由于不同来源土壤中Has的组成结构差异明显,它们对毒死蜱的吸附/解吸规律表现出不同的特征.土壤Has对毒死蜱的吸附/解吸行为的影响是多种因素综合作用的结果,具体作用机理尚待进一步研究.     

Degradation reactions of a carbamate herbicide, chlorbufam: effect of soil factors

Kinetics of degradation of chlorbufam is determined in aqueous solution, in aqueous solution with humic acids, argilo-humic complexes, soil and sterile soil. The adsorption is also evaluated in this different fractions. The adsorption process has a protecting effect and the chlorbufam is not chemically degraded when it is adsorbed on organic matter. The biodisponibility is also decreased by adsorption.     

Adsorption studies of the herbicide simazine in agricultural soils of the Aconcagua valley, central Chile

Simazine is a s-triazine herbicide that has been applied worldwide for agriculture. This herbicide is the second most commonly detected pesticide in surface and groundwater in the United States, Europe and Australia. In this study, simazine adsorption behaviour was studied in two agricultural soils of the Aconcagua valley, central Chile. The two studied soils were soil A (loam, 8.5% organic matter content) and soil B (clay-loam, 3.5% organic matter content). Three times higher simazine adsorption capacity was observed in soil A (68.03 mg kg⁻¹) compared to soil B (22.03 mg kg⁻¹). The simazine adsorption distribution coefficients (K_d) were 9.32 L kg⁻¹ for soil A and 7.74 L kg⁻¹ for soil B. The simazine adsorption enthalpy in soil A was −21.0 kJ mol⁻¹ while in soil B the adsorption enthalpy value was −11.5 kJ mol⁻¹. These results indicate that simazine adsorption process in these soils is exothermic, governing H bonds the adsorption process of simazine in both the loam and clay-loam soils. These results and the potentiometric profiles of both soils, suggest that simazine adsorption in soil A is mainly governed by simazine–organic matter interactions and in soil B by simazine–clay interactions. The understanding of simazine sorption–desorption processes is essential to determine the pesticide fate and availability in soil for pest control, biodegradation, runoff and leaching.     

Adsorption and desorption variability of four herbicides used in paddy rice production

This investigation was performed to determine the effect of physicochemical soil properties on penoxsulam, molinate, bentazon, and MCPA adsorption–desorption processes. Four soils from Melozal (35° 43′ S; 71° 41′ W), Parral (36° 08′ S; 71° 52′ W), San Carlos (36° 24′ S; 71° 57′ W), and Panimavida (35° 44′ S; 71° 24′ W) were utilized. Herbicide adsorption reached equilibrium after 4 h in all soils. The Freundlich L-type isotherm described the adsorption process, which showed a high affinity between herbicides and sorption sites mainly because of hydrophobic and H-bonds interaction. Penoxsulam showed the highest adsorption coefficients (4.23 ± 0.72 to 10.69 ± 1.58 mL g^?1) and were related to soil pH. Molinate showed K_d values between 1.72 ± 0.01 and 2.3 ± 0.01 mL g^?1and were related to soil pH and organic matter, specifically to the amount of humic substances. Bentazon had a high relationship with pH and humic substances and its K_d values were the lowest, ranging from 0.11 ± 0.01 to 0.42 ± 0.01 mL g^?1. MCPA K_d ranged from 0.14 ± 0.02 to 2.72 ± 0.01 mL g^?1, however its adsorption was related to humic acids and clay content. According to these results, the soil factors that could explain the sorption process of the studied herbicides under paddy rice soil conditions, were principally humic substances and soil pH. Considering the sorption variability observed in this study and the potential risk for groundwater contamination, it is necessary to develop weed rice management strategies that limit use of herbicides that exhibit low soil adsorption in areas with predisposing conditions to soil leaching.     

Removal of organic polyelectrolytes and their metal complexes by adsorption onto xonotlite

Natural organic polyelectrolytes (humic and fulvic acids) and their metal complexes were removed by adsorption onto xonotlite. The removal percentages of humic and fulvic acids by xonotlite were approximately 80% and 30%, respectively. Humic acid removal from solution by adsorption onto xonotlite took place more readily than fulvic acid removal. The molecular weight distributions of the humic substances remaining in solution after adsorption with the xonotlite were measured with size exclusion chromatography. A comparison of molecular weight distributions demonstrated conclusively that large molecular weight components were adsorbed preferentially, indicating that adsorption efficiency depends on the number of functional groups of humic substances. Furthermore, the surface topography of the adsorbent was observed before and after adsorption by scanning electron microscopy. The calculated heat of adsorption was of 330 kJ mol(-1) which was evaluated from the Clapeyron-Clausius equation. Therefore, the adsorption type can be considered chemical. Since xonotlite can be easily synthesized and obtained at low cost, the adsorption method of humic and fulvic acids is superior to their precipitation.     

Effect of pH and the role of organic matter in the adsorption of isoproturon on soils

Equilibrium measurements were carried out with the herbicide isoproturon on natural adsorbents (brown forest-, chernozem-, sandy soils and quartz) in different buffered media (pH 5, 7, 8 phosphate buffer). Adsorption isotherms were fitted by a multi-step adsorption equation providing numerical information used in the environmental propagation models and risk assessment works. In the adsorption of the slightly polar isoproturon the dissolved organic matter of the soil and the pH play an important role. At molecular level, results are interpreted by taking into consideration the hydrophobic interaction and the formation of hydrogen bonds between the surface and the solute. The observed adsorption behavior indicates that the organic matter content of the soils and its soluble fulvic acid, alkaline soluble humic acid and insoluble humin fractions were considerable different. The chernozem soil containing the highest amount of insoluble organic fraction proved to be a very efficient adsorbent. The brown forest and the sandy soils exhibit rather similar adsorbent properties but at pH 7 the latter containing more fulvic acid adsorbs less isoproturon due to the enhanced solubility of the soil organic matter. In alkaline conditions the negatively charged solute and the surface repel each other and the hydrophobic interactions are also weaker than in neutral media.     

The degradation of anilazine and dihydroxy‐anilazine at various soil depths of an orthic luvisol

Abstract

In conformity with Guideline 4.1 of the Federal German Biological Agency, degradation experiments with the fungicide active ingredient [benzene ring‐U‐¹⁴C]anilazine and its major metabolite [triazine ring‐U‐¹⁴C]dihydroxy‐anilazine were carried out in an orthic luvisol. Mineralization of the benzene ring carbon of anilazine amounted to less than 2 % in 110 days and that of the triazine ring carbon of dihydroxy‐anilazine to less than 8 %. Increasing the incubation temperature from 22 °C to 30 °C and adding organic substance influenced the mineralization slightly. In soils which received two or three applications in succeeding years with subsequent ageing in the open‐air lysimeter no stimulation of the mineralization was observed. Extractions after incubation showed that only 10.2 to 18.6 % of the ¹⁴C‐activity applied with anilazine was extractable with acetone/CaCl₂. The major proportion was bound in the fractions of the soil organic matter, namely 45.0 to 59.6 % of the radiocarbon applied was accounted for by the humin fraction, 12.0 to 27.4 % by the fulvic acids, and 9.4 to 15.0 % by the humic acids. In the case of dihydroxy‐anilazine, 28.9 to 89.7 % of the applied ¹⁴C‐activity was extractable with acetone/CaCl₂. Of tJhe radiocarbon bound in the soil, the greatest proportion, i.e. 18.5 to 35.5 % of the radiocarbon applied, was accounted for by the fulvic acids.     

Effects of organic acids on adsorption of lead onto montmorillonite,goethite and humic acid

Adsorption isotherms for Pb onto six soil components (quartz, feldspar, kaolinite, montmorillonite, goethite and humic acid) were studied. The influence of pH, EDTA and citric acid on the adsorption of Pb onto montmorillonite, goethite and humic acid were considered. Results indicate that the experimental data fit the Langmuir Adsorption Isotherm. The adsorption capacity for Pb at pH 6 was found to be in the order: humic acid (22.7 mg g(-1)) > goethite (11.04 mg g(-1)) > montmorillonite (10.4 mg g(-1)) > kaolinite (0.91 mg g(-1)) > feldspar (0.503 mg g(-1)) > quartz (0.148 mg g(-1)). Generally, the amount of Pb adsorbed onto montmorillonite, goethite and humic acid decreased with increasing concentrations of EDTA and citric acid and with increases in alkality. However, there were two exceptions: (1) addition of citric acid increased the amount of Pb adsorbed onto humic acid; and (2) the amount of Pb adsorbed onto goethite decreased with increasing pH in the presence of EDTA. Some mechanisms involved in the adsorption reactions are discussed.     

Copper binding by peat fulvic and humic acids extracted from two horizons of an ombrotrophic peat bog

We studied the binding of Cu(II) to humic acids and fulvic acids extracted from two horizons of an ombrotrophic peat bog by metal titration experiments at pH 4.5, 5.0, 5.5, and 6.0 and 0.1 M KNO3 ionic strength. Free metal ion concentrations in solution were measured using an ion selective electrode. The amounts of base required to maintain constant pH conditions were recorded and used to calculate H+/Cu2+ exchange ratios. The amount of Cu(II) bound to the humic fractions was greater than the amount bound to the fulvic fractions and only at the highest concentrations of metal ion the amount of Cu(II) sorbed by both fractions became equal. The proton to metal ion exchange ratios are similar for all humic substances, with values ranging from 1.0 to 2.0, and decreasing with increased pH. The amount of Cu(II) bound is practically independent of the horizon from which the sample was extracted. The results indicate that the humic substances show similar cation binding behaviour, despite the differences in chemical composition. The copper binding data are quantitatively described with the NICA-Donnan model, which allows to characterize only the carboxylic type binding sites. The values of the binding constants are higher for the humic acids than for the fulvic acids.     

Kinetics of simazine advanced oxidation in water

Abstract

Comparison of the effects and kinetics of UV photolysis and four advanced oxidation systems (ozone, ozone/hydrogen peroxide, ozone/UV radiation and UV radiation/hydrogen peroxide) for the removal of simazine from water has been investigated. At the conditions applied, the order of reactivity was ozone < ozone/hydrogen peroxide < UV radiation < ozone/UV radiation and UV radiation/hydrogen peroxide. Rate constants of the reactions between ozone and simazine and hydroxyl radical and simazine were found to be 8.7 M^‐1s^‐1 and 2.1x10⁹ M^‐1s^‐1, respectively. Also, a quantum yield of 0.06 mol.photon^‐1 was found for simazine at 254 nm UV radiation. The high value of the quantum yield corroborated the importance of the direct photolysis process. Percentage contributions of direct reaction with ozone, reaction with hydroxyl radicals and direct photolysis were also quantified.     

Surface charge and adsorption from water onto quartz sand of humic acid

The surface charge of humic acid under different conditions of ionic strength, pH, and the presence of various cationic ions (Cu(2+), Zn(2+), Ba(2+), and Ca(2+)) was determined by a titration method using a cationic polyelectrolyte as titrant. Adsorption isotherms in batch experiments of the polymer from water onto quartz sand were determined at 20 degrees C, 40 degrees C, and 60 degrees C and under different conditions of ionic strength, pH, and the presence of various cationic ions (Cu(2+), Zn(2+), Ba(2+), and Ca(2+)). The data indicate significant decrease of humic acid surface charge by decreasing the pH value from 10.0 to 4.1. Similar decrease of humic acid surface charge was observed by increasing either the ionic strength or the affinity of the divalent cation toward the humic acid. At ambient temperature the adsorption of humic acid on the quartz sand seems to be controlled mainly by electrical interaction between the organic particle and the solid substrate. A correlation is found between the surface charge and the adsorbed amount of the polymer, the adsorbed amount increases when the surface charge of humic acid decreases. The increase of the adsorbed amount with the temperature suggests that adsorption process is endothermic.     

Removal of Alachlor from Water by Catalyzed Ozonation in the Presence of Fe2+, Mn2+, and Humic Substances

Abstract

The effects of Fe(II), Mn(II) and humic substances on the catalyzed ozonation of alachlor, an endocrine disruptor were investigated. Results revealed that small amounts of Fe(II), Mn(II), and humic substances could enhance the ozonation of alachlor, but larger amounts of them would retard the oxidation. These results were successfully identified by an electron paramagnetic resonance (EPR) spectroscopy/spin-trapping method that could quantify hydroxyl radicals. The production of hydroxyl radicals was obviously increased with the increasing of Fe(II) concentration, which contributed to enhance ozonation at low concentrations. But the excess Fe(II) consumed some of the radicals when it was added at a higher concentration (1.5 mg/L). However, no obvious radicals were observed when a different amount of Mn(II) was used, and the catalytic ozonation of alachlor by Mn(II) mainly followed the mechanism of “active sites created on the surface of MnO₂.” The radical pathway was followed when alachlor was ozonated with different concentrations of humic substances because of its radical initiating, promoting, and inhibiting effects.     

Effects of pollution on humic substances

Abstract

To assess effects of industrial and environmental pollution on analytical characteristics of humic substances, we isolated humic acids (HA's) and fulvic acids (FA's) from unpolluted and polluted soils and sediments. Following purification, the HA's and FA's were characterized by elemental (C, H, O, N, S) and functional group (CO₂H, phenolic OH, total acidity) analyses, infrared (IR) spectrophotometry, differential thermal analysis (DTA) and by metal (Fe, Al, Cu, Mn, Pb, Ni, Co, Zn, Cr, Cd, Hg, Ca and Mg) analyses. Si was also determined in all samples.

Polluted HA's and FA's contained more N and S but less 0 and were richer in all metals and Si than were unpolluted ones. IR spectra showed that polluted humic materials were enriched in COO^‐ groups, secondary non‐cyclic amides and possible also in SO₃H groups. DTA curves indicated that polluted HA's and FA's were more thermostable than unpolluted HA's and FA's. Unusually high N, S, Cu, Cr, Zn and Hg contents of humic materials appear to be useful indicators of soil and sediment pollution.     

Soil pH and Anion Abundance Affects on Copper Adsorption

Abstract

Copper (Cu) input to agricultural soils results from Cu containing pesticides and/or that in soil amendments, such as manure or sewage sludge. Soil and soil solution properties influence the adsorption and desorption of Cu by the soil, which in turn determines its plant availability and/or phytotoxicities. Effects of different anion enrichment in the equilibrium solution on Cu adsorption by different soils (pH range of 6.2–9.9) were investigated in this study over a range of Cu concentrations. With Cu concentrations in the range of 0–100 mg L^?1 in the equilibration solution, 95–99% of applied Cu was adsorbed by all three soils. The adsorption of Cu was similar regardless of using either 0.01 M CaCl₂ or Ca(NO₃)₂ as the equilibration solution. When the Cu concentration in the equilibration solution was further increased in the range of 500–2000 mg L^?1, the adsorption of Cu decreased from 60 to 24% of applied Cu in two soils with pH 6.2–7.9. In a high pH soil (pH = 9.9), the Cu adsorption decreased from 77 to 34%. Addition of incinerated sewage sludge (ISS) to a Palouse silt loam soil (pH = 6.2) increased the Cu adsorption as compared to that by unamended soil. This was, in part, due to an increase in the soil suspension pH with ISS amendment.     

In vitro study of oxytetracycline adsorption on activated charcoal

Abstract

In vitro adsorption experiments simulating pH in gastric environment and using Langmuir isotherm, showed that 408 mg of oxytetracycline was adsorbed per gram of activated charcoal. Langmuir isotherm fitted adsorption data better than a Freundlich isotherm. Freundlich isotherm showed a specific adsorption capacity of 518 mg/g for activated charcoal. Both isotherm parameters indicated a strong oxytetracycline adsorption on activated charcoal in terms of quantity and binding strength. The results demonstrate that the concomitant use of oxytetracyline and activated charcoal should be avoided.