Influence of rhamnolipids and triton X-100 on the desorption of pesticides from soils

A rhamnolipid biosurfactant mixture produced by P. aeruginosa UG2 and the surfactant Triton X-100 were tested for their effectiveness of enhancing the desorption of trifluralin, atrazine, and coumaphos from soils. Sorption of both surfactants by the soils was significant and adequately described by the Langmuir-type isotherm. Values of maximum sorption capacity (Qmax) and Langmuir constant (Klang) did not correlate with the amount of soil organic matter. Our results indicate that clay surfaces play an important role in the sorption of surfactants. When surfactant dosages were high enough to reach soil saturation and maintain an aqueous micellar phase, pesticide desorption was only enhanced. At dosages below soil saturation, surfactants sorbed onto soil, increasing its hydrophobicity and enhancing the sorption of the pesticides by a factor of 2. Similar values of water-soil partition coefficients (Ksol*) for aged and fresh added pesticides to soils indicate that the aging process used did not significantly after the capability of either surfactant to desorb the pesticides. A model able to estimate equilibrium distributions of organic compounds in soil-aqueous-micellar systems was tested against experimental results. The determined organic carbon partition coefficients, Koc values, indicate that, on a carbon normalized basis, sorbed Rh-mix is a much better sorbent of pesticides than TX-100 or soil organic matter. These results have significant implications on determining the effectiveness of surfactants to aid soil remediation technologies.     

Evaluation of growth activity of microbes in tea field soil using microbial calorimetry

Calorimetry was used to study the heat evolution associated with microbial growth in tea field soils (growth thermograms) during the microbial degradation of added organic matter. From the actual heat evolution curves (f(t) curves) derived from the growth thermograms under various conditions of pH and water content of the tea field soils, the apparent growth rate constant (mu') of soil microbes was determined as an index of their growth activity. In addition, mu' was compared between tea field soils treated with organic versus compound fertilizer. From the results, the following conclusions were made: (i) In acidic tea field soil (pH less than about 6.0), the growth activity of soil microbes declined with decreasing pH, and mu' was twofold higher at pH 6.0 than at pH 4.3. (ii) In tea field soils (Andosol) with a water content less than about 50%maximum water holding capacity (MWHC), the growth activity declined with decreasing water content, and mu' at 52.5%MWHC was double that at 35.2%MWHC. (iii) The growth activity of microbes in tea field soil treated with organic fertilizer was approximately 1.2-fold higher than that treated with compound fertilizer.     

Sorption-controlled degradation kinetics of MCPA in soil

The relationship between sorption strength and degradation kinetics has been studied for the pesticide MCPA in a sandy top- and subsoil. After adding two types of sorbents (crushed peat and activated carbon) in various amounts to the sandy soils, sorption, desorption, and mineralization of 14C-MCPA were measured. The obtained Freundlich constants (KF) varied between 0.7 and 27.2 mg(1-nF) x L(nF)/kg, and the first-order mineralization rate constants varied between 0.001 and 0.128 d(-1). The results showed an inverse relationship between sorption strength and mineralization. A higher KF value corresponded to a smaller mineralization rate and less mineralization. A correlation coefficient of r2 = 0.934 between the log-transformed Freundlich desorption coefficient (K(F,des)) and the log-transformed mineralization rate constant (k) was obtained. After 7, 14, 22, and 35 days of incubation, soil samples were consecutively extracted by water, methanol, and 5 M NaOH to separate the remaining 14C into 3 different pools. The extractions showed that the mineralization only proceeded from the water extractable pool of MCPA. Thin-layer chromatography revealed a formation of small amounts of metabolites; <7% of initially added 14C was present as other compounds than 14C-MCPA in the water and methanol extractable pools. The study showed mineralization to be strongly correlated with sorption, represented by the desorption coefficient, and hence stresses the significance of bonding strength for estimating pesticide degradation in soil.     

Fate of pesticides in the arid subtropics, Botswana, Southern Africa

Despite a history of pesticide usage, few data exist on their concentrations in air and soil of Southern Africa. To add to the understanding of the processes controlling the fate of organic contaminants in arid regions, the levels, spatial trends, and seasonal variability of pesticides were studied in air and soil from Botswana. XAD resin-based passive air samplers (PAS) were deployed at 15 sites across the country from May 2006 to May 2007. Soil samples were collected from the vicinity of nine of the PAS sampling sites. In addition, 27 24-h high-volume air samples were collected in Maun, at the southeastern edge of the Okavango Delta, every two weeks for one year. Levels of pesticides in PAS were low, with α-endosulfan and lindane being most abundant. Concentrations in soils were extremely low and only soils with high organic carbon contained notable amounts of dieldrin and traces of other pesticides. In particular, air and soil from the Okavango Delta had very low levels even though the area had repeatedly been sprayed with DDT and endosulfan in the past. Air samples from Eastern Botswana, where the majority of the population lives, contained higher levels. Higher air concentrations of α-endosulfan occurred during summer and higher HCB levels occurred in winter. This seasonality was related with neither minor seasonal changes in temperature nor hydrological seasonal events such as the rainy season or the flooding of the Okavango Delta. Thus, the observed spatial and seasonal patterns are more likely related to pesticide usage pattern than to environmental factors or historical use. High temperature and low organic matter content limit the uptake capacity of most subtropical soils for pesticides. No evidence was found that sorption to dry mineral matter plays a major role. Arid soils in subtropical regions are therefore neither a major reservoir of organic contaminants nor do they constitute a significant long-term source of pesticides to the atmosphere.     

Emission of chiral organochlorine pesticides from agricultural soils in the cornbelt region of the U.S

Several organochlorine pesticides are chiral molecules manufactured as racemic mixtures. Past research has shown that selective degradation of pesticide enantiomers by microorganisms occurs resulting in nonracemic signatures in soils. In this work, volatilization of chiral pesticides from soil was investigated to determine if enantioselective breakdown in soils could be used as a source signature to track releases of chiral pesticides to the atmosphere. Air samples were taken directly above agricultural soils at several sites, and enantiomeric signatures were found to be nonracemic following patterns found in the soil. A follow up study at one site showed that for most compounds concentration decreased with increasing height above the soil, while enantiomer fractions for chiral pesticides were similar to that found in the soil, signifying the soil as a source to the air. The enantiomer fractions of ambient air samples from rural nonagricultural areas in the region were also found to be nonracemic.     

Effect of two organic amendments on norflurazon retention and release by soils of different characteristics

The influence of two organic amendments on norflurazon sorption-desorption processes in four soils with very different physicochemical characteristics was studied in laboratory experiments to evaluate the potential leaching of this pesticide through organic fertilized soils. Sorption-desorption experiments were performed on original soils and on a mixture of these soils with urban waste compost (SUW) and a commercial amendment from olive-mill wastes (OW), at a rate of 6.25% (w/w). These mixtures were used immediately after preparation and after aging for 2 months. Norflurazon was analyzed by using a HPLC method. Norflurazon retention in original soils was related not only to the organic matter (OM) content but also to mineral surfaces present in soils. Norflurazon sorption increases largely after amendment in soils with low OM content, but the addition of exogenous OM to soils with medium OM content and/or other available adsorptive surfaces did not significantly affect norflurazon sorption. Even in some cases pesticide sorption decreases, due to the blocking of the mineral and organic soil surfaces with the amendment added. Transformation of exogenous OM during incubation depends both on the amendment added and on the type of soil and can affect sorption-desorption behavior of the soils surfaces in different manner, due to the modification of their hydrophobic-hydrophilic characteristics. Norflurazon desorption from original soils showed hysteresis in all cases, but it was not affected or even decreased in amended soils. It was a nonexpected behavior, especially in sandy soil, since it is generally assumed that a higher sorption always implies a lower mobility in soils. Norflurazon sorption must be taking place on very low affinity sites on exogenous OM through weak bindings, from which the pesticide can be easily desorbed. The application to soils of the organic amendments used in the present study could not be accepted to reduce norflurazon losses due to leaching processes.     

Molecular interactions of pesticides at the soil-water interface

High-resolution magic angle spinning (HR-MAS) NMR spectroscopy combined with saturation-transfer double difference (STDD) NMR can be used to analyze the molecular-level interactions of pesticides and whole soils occurring at the soil-water interface. Here 1H HR-MAS STDD NMR has been applied to some common pesticides (trifluralin, acifluorfen, and (4-nitro-3-(trifluoromethyl) phenol) and a pesticide degradation product (1-naphthol). Results indicate that dipolar interactions, H-bonding, hydrophobic associations, and potentially pi-pi interactions are the predominant sorption mechanisms for these molecules at the soil-aqueous interface. It is evident that the physical and chemical characteristics of soil are highly influential in determining the mechanisms of pesticide sorption, as they significantly affect soil conformation. In particular, different binding mechanisms were observed for 1-naphthol in soil swollen using a buffer versus D2O, indicating that the K(oc) alone may not be enough to accurately predict the behavior of a molecule in a real soil environment. Preliminary kinetic-based studies suggest that both the swelling solvent and soil moisture content significantly influence the sequestration of trifluralin. These studies demonstrate that HR-MAS and STDD NMR are powerful and versatile tools which can be applied to expand our knowledge of the mechanistic interactions of agrochemicals at the molecular level.     

Speciation of Se and DOC in soil solution and their relation to Se bioavailability

A 0.01 M CaCl(2) extraction is often used to asses the bioavailability of plant nutrients in soils. However, almost no correlation was found between selenium (Se) in the soil extraction and Se content in grass. The recently developed anion Donnan membrane technique was used to analyze chemical speciation of Se in the 0.01 M CaCl(2) extractions of grassland soils and fractionation of DOC (dissolved organic carbon). The results show that most of Se (67-86%) in the extractions (15 samples) are colloidal-sized Se. Only 13-34% of extractable Se are selenate, selenite and small organic Se (<1 nm). Colloidal Se is, most likely, Se bound to or incorporated in colloidal-sized organic matter. The dominant form of small Se compounds (selenate, selenite/small organic compounds) depends on soil. A total of 47-85% of DOC is colloidal-sized and 15-53% are small organic molecules (<1 nm). In combination with soluble S (sulfur) and/or P (phosphor), concentration of small DOC can explain most of the variability of Se content in grass. The results indicate that mineralization of organic Se is the most important factor that controls Se availability in soils. Competition with sulfate and phosphate needs to be taken into account. Further research is needed to verify if concentration of small DOC is a good indicator of mineralization of soil organic matter.     

Extensive sorption of organic compounds to black carbon, coal, and kerogen in sediments and soils: mechanisms and consequences for distribution, bioaccumulation, and biodegradation

Evidence is accumulating that sorption of organic chemicals to soils and sediments can be described by "dual-mode sorption": absorption in amorphous organic matter (AOM) and adsorption to carbonaceous materials such as black carbon (BC), coal, and kerogen, collectively termed "carbonaceous geosorbents" (CG). Median BC contents as a fraction of total organic carbon are 9% for sediments (number of sediments, n approximately 300) and 4% for soils (n = 90). Adsorption of organic compounds to CG is nonlinear and generally exceeds absorption in AOM by a factor of 10-100. Sorption to CG is particularly extensive for organic compounds that can attain a more planar molecular configuration. The CG adsorption domain probably consists of surface sites and nanopores. In this review it is shown that nonlinear sorption to CG can completely dominate total sorption at low aqueous concentrations (<10(-6) of maximum solid solubility). Therefore, the presence of CG can explain (i) sorption to soils and sediments being up to 2 orders of magnitude higher than expected on the basis of sorption to AOM only (i.e., "AOM equilibrium partitioning"), (ii) low and variable biota to sediment accumulation factors, and (iii) limited potential for microbial degradation. On the basis of these consequences of sorption to CG, it is advocated that the use of generic organic carbon-water distribution coefficients in the risk assessment of organic compounds is not warranted and that bioremediation endpoints could be evaluated on the basis of freely dissolved concentrations instead of total concentrations in sediment/soil.     

Vertical and lateral redistribution of POPs in soils developed along a hydrological gradient

Study of the dispersion of persistent organic pollutants (POPs) throughout the environment is necessitated by their toxicological properties and propensity to accumulate in biota. In this study, we use data from the analysis of three (210)Pb dated soil profiles collected along a 30-m hydrological gradient to demonstrate postdepositional mobility of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs). We found that (i) humus originating from litter exposed to surface fallout during the 1960-1970s contains the highest concentrations of PCDD/Fs and PCBs in the O-horizon of the soils; (ii) accumulation rates of PCDD/Fs and PCBs in the O-horizon (～5.0 and ～210 μg m(-2) yr(-1)) constituted only 9.1% and 3.5%, respectively, of the measured annual input, demonstrating that a minor fraction of the deposited material is retained within the O-horizon; (iii) POP inventories in the upper 0.5-0.9 m of the mineral soil constituted a considerable part (40-70%) of the total pool stored in the soil, implying significant vertical translocation of atmospheric derived POPs; and (iv) increasing downslope inventories of POPs suggest a lateral downward transport of POPs from uphill soils. The findings challenge the commonly accepted view that POPs fallout is effectively retained within O-horizons.     

Prediction of the processing factor for pesticides in apple juice by principal component analysis and multiple linear regression

The main objective of this work was to establish a mathematical function that correlates pesticide residue levels in apple juice with the levels of the pesticides applied on the raw fruit, taking into account some of their physicochemical properties such as water solubility, the octanol/water partition coefficient, the organic carbon partition coefficient, vapour pressure and density. A mixture of 12 pesticides was applied to an apple tree; apples were collected after 10 days of application. After harvest, apples were treated with a mixture of three post-harvest pesticides and the fruits were then processed in order to obtain apple juice following a routine industrial process. The pesticide residue levels in the apple samples were analysed using two multi-residue methods based on LC-MS/MS and GC-MS/MS. The concentration of pesticides was determined in samples derived from the different steps of processing. The processing factors (the coefficient between residue level in the processed commodity and the residue level in the commodity to be processed) obtained for the full juicing process were found to vary among the different pesticides studied. In order to investigate the relationships between the levels of pesticide residue found in apple juice samples and their physicochemical properties, principal component analysis (PCA) was performed using two sets of samples (one of them using experimental data obtained in this work and the other including the data taken from the literature). In both cases the correlation was found between processing factors of pesticides in the apple juice and the negative logarithms (base 10) of the water solubility, octanol/water partition coefficient and organic carbon partition coefficient. The linear correlation between these physicochemical properties and the processing factor were established using a multiple linear regression technique.     

湖南省主要植烟区域土壤有机氮矿化特性研究

以湖南主要烟区植烟土壤为研究对象,采用Warning 淹水培养法,对植烟土壤进行矿化培养试验,深入研究不同烟区土壤有机氮矿化特性。结果表明,湖南省植烟土壤有机氮矿化速率均表现为前期较快,后期缓慢。湘南、湘中、湘西植烟土壤有机氮矿化积累量、矿化速率、矿化势相差较大,且均表现为“湘中>湘南>湘西”。矿化氮与全氮、有机质线性回归结果显示,与矿化氮含量密切相关的依次为活性有机碳>全氮>有机质>腐殖质碳。总体表明,活性有机碳与矿化氮量密切相关,是矿化的主体。     

Simultaneous immobilization of lead and atrazine in contaminated soils using dairy-manure biochar

Biochar produced from waste biomass is increasingly being recognized as a green, cost-effective amendment for environmental remediation. This work was to determine the ability of biochar to immobilize heavy metal Pb and organic pesticide atrazine in contaminated soils. Biochar prepared from dairy manure was incubated with contaminated soils at rates of 0, 2.5, and 5.0% by weight for 210 d. A commercial activated carbon (AC) was included as a comparison. The AC was effective in immobilizing atrazine, but was ineffective for Pb. However, biochar was effective in immobilizing both atrazine and Pb and the effectiveness was enhanced with increasing incubation time and biochar rates. After 210 d, soils treated with the highest rate of 5.0% biochar showed more than 57% and 66% reduction in Pb and atrazine concentrations in 0.01 M CaCl(2) extraction, respectively. Lead and atrazine concentrations in the toxicity characteristic leaching procedure solutions were reduced by 70-89% and 53-77%, respectively. Uptake of Pb and atrazine by earthworms (Eisenia fetida) was reduced by up to 79% and 73%. Phosphorus originally contained in biochar reacted with soil Pb to form insoluble hydroxypyromorphite Pb(5)(PO(4))(3)(OH), as determined by X-ray diffraction, which was presumably responsible for soil Pb immobilization, whereas atrazine stabilization may result from its adsorption by biochar demonstrated by the significant exponential decrease of extractable atrazine with increasing organic C in biochar (r(2) > 0.97, p < 0.05). The results highlighted the potential of dairy-manure biochar as a unique amendment for immobilization of both heavy metal and organic contaminants in cocontaminated soils.     

A comparative evaluation of methodologies for water content determination in green coffee

The main objective of this study was to compare methods for mass loss evaluation in green coffee to water content determination by Karl Fischer titration (KFT). The following methodologies were tested: (i) ISO 6673 (oven drying at 105 °C for 16 h); (ii) the reference method employed by the Brazilian Agriculture Ministry (oven drying at 105 °C for 24 h)—BRAMw, employing whole beans and BRAMg, employing ground beans; and (iii) infrared drying (IRD). Reference oven drying methodologies ISO 6673 and BRAMw presented results statistically equivalent (p>0.05) to those from KFT in the moisture content range that is of interest for green coffee commercialization (8-13 g/100 g), whereas IRD results were lower than those for KFT. ISO 6673 and BRAMw also presented the highest values of correlation coefficients to KFT. Differences in moisture content determination became more significant for lower moisture content values (4-7 g/100 g), probably due to loss of organic volatile substances during drying and occurrence of moisture loss during sample grinding.     

云南曲靖烟区典型植烟土壤氮素矿化规律研究

以云南曲靖烟区的主要植烟土壤为研究对象,采用Warning淹水培养方法,研究了不同类型土壤的氮素矿化过程。结果表明,淹水培养0-14 d宣威水稻土、罗平黄壤、罗平红壤、宣威红壤和宣威紫色土土壤铵态氮含量迅速增加,此期间的氮累积矿化量约占最高氮矿化量的83.7%。14 d后,宣威水稻土、罗平黄壤、宣威红壤和罗平红壤土壤铵态氮含量缓慢增加,表现为氮素的持续矿化;罗平红壤培养28 d土壤铵态氮含量达到最高值,其他3个土壤在42 d达到最高值;而宣威紫色土在14 d后土壤铵态氮含量持续减少,表现为氮素的固定。培养过程中(除42 d外),土壤铵态氮含量均表现为罗平黄壤、宣威水稻土>宣威红壤>罗平红壤>宣威紫色土。土壤氮累积矿化速率随培养时间逐渐降低且符合对数函数,罗平黄壤最高,宣威紫色土最低。罗平黄壤、宣威水稻土、罗平红壤土壤氮矿化率随培养时间逐渐增加,罗平黄壤的土壤氮矿化率最高,宣威紫色土最低。说明罗平黄壤和宣威水稻土的供氮能力较强,生产中应适当降低氮肥用量;宣威紫色土的供氮能力较弱,生产中适当补充氮肥,促进烟苗生长。     

Review: Use of recycled wastewater for irrigating grapevines

Municipal and winery wastewater can provide a valuable irrigation source in regions where water accessibility is problematic or sustainable disposal of waste is essential. It is imperative, however, that when used for irrigation, water conservation benefits are not compromised by a decline in soil and plant health. To date, published literature investigating the use of wastewaters for grapevine production is restricted to a limited set of studies. Globally, wastewater usage within the horticultural sector, including winegrape production, is increasing. It is necessary, therefore, to better understand the short‐ and long‐term implications of such practice. Although wastewaters may contain a range of organic and inorganic pollutants, this review focuses primarily on specific issues associated with high salt loading that is typical under wastewater irrigation. Managing salt, in particular sodium (Na⁺) and potassium (K⁺), in wastewater will be necessary in order to maintain the soil physical, chemical and biological health in the long term. Soil structural degradation resulting from a high concentration of exchangeable monovalent cations is of major concern where wastewater is being used for irrigation. This review will address (i) the effect of wastewater irrigation on vine performance and grape quality; (ii) chemical and physical changes in soils irrigated with municipal and winery wastewater; and (iii) management practices that may assist in ameliorating vineyard soils abundant in monovalent cations as a result of wastewater irrigation.     

Assessing the relationship between extensive use of organochlorine pesticides and cooling trend during the mid-20th century in the southeastern United States

In contrast to global warming, temperatures in the southeastern United States have exhibited a decreasing trend of up to 1-2 degrees C over the last century. We investigated the relationship between this cooling trend and the extensive use of organochlorine pesticides--particularly dichloro-diphenyl-trichloroethane (DDT) and toxaphene--in the southeastern U.S. from the mid-1940s through the 1970s. Based on annual use and soil residue estimates, it is shown that enthalpies associated with the endothermic evaporation of pesticides from soil resulted in surface temperature decreases of up to -0.2 degrees C. This is the first study to show the inverse correlation between surface air temperature and pesticide use. These findings highlight the potential contribution of the extensive use of organochlorine pesticides to changes in the surface air temperature, especially in regions of intensive agriculture and pesticide use.     

吸胀期低温与水分条件对油菜种子萌发的耦合效应

为了探讨晚播油菜适宜播种的田间温度和水分条件,以华杂62和华双5号品种为材料,在土壤和PEG溶液两种介质中研究了吸胀温度与水势对种子萌发的影响。结果表明,吸胀期温度和水分条件对油菜种子的萌发具有显著影响。在5～15℃范围内,种子萌发活力随吸胀期土壤温度的升高而提高。在10℃和15℃下吸胀,土壤相对含水量为58．6％、水势为-0．1MPa时较适宜于种子萌发;在5℃低温下吸胀,适当降低土壤水势有利于种子萌发。华杂62种子具有吸胀冷害现象,在低温和高水势下吸胀,种子萌发活性降低,吸水速度加快,种子浸泡液K^＋渗漏量升高,而Na^＋渗漏量和Na^＋／K^＋比值降低。华双5号种子则具有较强的抗吸胀冷害能力,表现为在低温下吸胀受水势的影响较小。     

Sediment-water distribution of organic contaminants in aquatic ecosystems: the role of organic carbon mineralization

The distribution between sediments and water plays a key role in the food-chain transfer of hydrophobic organic chemicals. Current models and assessment methods of sediment-water distribution predominantly rely on chemical equilibrium partitioning despite several observations reporting an "enrichment" of chemical concentrations in suspended sediments. In this study we propose and derive a fugacity based model of chemical magnification due to organic carbon decomposition throughout the process of sediment diagenesis. We compare the behavior of the model to observations of bottom sediment-water, suspended sediments-water, and plankton-water distribution coefficients of a range of hydrophobic organic chemicals in five Great Lakes. We observe that (i) sediment-water distribution coefficients of organic chemicals between bottom sediments and water and between suspended sediments and water are considerably greaterthan expected from chemical partitioning and that the degree sediment-water disequilibrium appears to follow a relationship with the depth of the lake; (ii) concentrations increase from plankton to suspended sediments to bottom sediments and follow an inverse ratherthan a proportional relationship with the organic carbon content and (iii) the degree of disequilibrium between bottom sediment and water, suspended sediments and water, and plankton and water increases when the octanol-water partition coefficient K(ow) drops. We demonstrate that these observations can be explained by a proposed organic carbon mineralization model. Our findings imply that sediment-water distribution is not solely a chemical partitioning process but is to a large degree controlled by lake specific organic carbon mineralization processes.