Combined effect of diuron and simazine on photosystem II photochemistry in a sandy soil and soil amended with solid olive-mill waste

Diuron (3-(3,4-dichlorophenyl)- = 1,1-dimethylurea) and simazine (6-chloro-N(2), N(4)-diethyl-1,3,5-triazine-2,4-diamine) are soil-applied herbicides used in olive crops. The objective of this study is to investigate the effect of these herbicides on Photosystem II photochemistry of Olea europaea L., and whether the amendment of soil with an organic waste (OW) from olive oil production industry modifies this effect. For this purpose, herbicide soil adsorption studies, with unamended and OW-amended soil, and chlorophyll fluorescence measurements in adult olive leaves, after one, two and three weeks of soil herbicide treatment and/or OW amendment, were performed. Soil application of these herbicides reduced the efficiency of Photosystem II photochemistry of olive trees due to chronic photoinhibition, and this effect is counterbalanced by the addition of OW to the soil. OW reduces herbicide uptake by the plant due to an increase in herbicide adsorption.     

Combined effect of diuron and simazine on photosystem II photochemistry in a sandy soil and soil amended with solid olive-mill waste

Diuron (3-(3,4-dichlorophenyl)- = 1,1-dimethylurea) and simazine (6-chloro-N ², N ⁴-diethyl-1,3,5-triazine-2,4-diamine) are soil-applied herbicides used in olive crops. The objective of this study is to investigate the effect of these herbicides on Photosystem II photochemistry of Olea europaea L., and whether the amendment of soil with an organic waste (OW) from olive oil production industry modifies this effect. For this purpose, herbicide soil adsorption studies, with unamended and OW-amended soil, and chlorophyll fluorescence measurements in adult olive leaves, after one, two and three weeks of soil herbicide treatment and/or OW amendment, were performed. Soil application of these herbicides reduced the efficiency of Photosystem II photochemistry of olive trees due to chronic photoinhibition, and this effect is counterbalanced by the addition of OW to the soil. OW reduces herbicide uptake by the plant due to an increase in herbicide adsorption.     

Effect of herbicide and soil amendment on growth and photosynthetic responses in olive crops

Diuron [3-(3,4-dichlorophenyl)- = 1,1-dimethylurea] and simazine (6-chloro-N(2), N(4)-diethyl-1,3,5-triazine-2,4-diamine) are soil-applied herbicides used in olive crops. The objective of this study is to investigate the combined effect of these herbicides and the amendment of soil with an organic waste (OW) from the olive oil production industry on the growth and photosynthetic apparatus of adult olive trees and to compare the results with those obtained by Redondo-Gómez et al. for two-year-old trees. For this purpose, growth rate, gas exchange and chlorophyll fluorescence parameters were measured in 38-year-old olive trees, after one and two months of soil herbicide treatment and/or OW amendment. Soil co-application of OW and herbicide increases the quantum efficiency of Photosystem II (PSII) and the assimilation of CO(2) in olive trees, which led to a higher relative growth rate of the branches and leaves in length. Herbicide treatment reduced the photosynthetic efficiency in olive trees after two months of soil application, while this reduction is evident from week one in younger trees.     

Direct measurement of octanol-water partition coefficients of some environmentally relevant brominated diphenyl ether congeners

Octanol-water partition coefficients (K(OW)) of nine environmentally relevant brominated diphenyl ether (BDE) congeners present in two technical mixtures were directly measured using a slow-stir technique. LogK(OW) values of tri- to heptabrominated BDE congeners ranged from 5.74 to 8.27, and were related to bromine content by the equation logK(OW)=0.621(#Br)+4.12(R(2)=0.970). The directly determined K(OW) values were generally lower than those calculated using fragment constant methods, particularly at higher levels of bromine substitution. The quasi-experimental approach of using fragment constants to modify a "backbone" compound of known K(OW) was much more successful than using the fragment constants to "build" the entire molecule. The tri- and tetrabrominated congeners are in the range of optimum bioaccumulation potential.     

Estimating octanol-air partition coefficients with octanol-water partition coefficients and Henry's law constants

The octanol-air partition coefficient (K(OA)) is useful for predicting the partitioning behavior of organic compounds between air and environmental matrices such as soil, vegetation, and aerosol particles. At present, experimentally determined K(OA) values are available for only several hundred compounds. Therefore, the ability to estimate K(OA) is necessary for screening level evaluation of most chemicals. Although it is possible to estimate K(OA) from the octanol-water partition coefficient (K(OW)) and Henry's law constant (HLC), various concerns have been raised in regard to the usability of this estimation methodology. This work examines the accuracy and usability of K(OW) and HLC in application to a comprehensive database set of K(OA) values for screening level environmental assessment. Results indicate that K(OW) and HLC can be used to accurately predict K(OA) even when estimated K(OW) and HLC values are used. For an experimental dataset of 310log K(OA) values for different compounds, the K(OW)-HLC method was statistically accurate as follows: correlation coefficient (r2): 0.972, standard deviation: 0.526, absolute mean error: 0.358 using predominantly experimental K(OW) and HLC values. When K(OW) and HLC values were estimated (using the KOWWIN and HENRYWIN programs), the statistical accuracy was: correlation coefficient (r2): 0.957, standard deviation: 0.668, absolute mean error: 0.479.     

Salting-in and salting-out effects of ionic and neutral osmotica on limonene and linalool Henry's law constants and octanol/water partition coefficients

Foliar emission rates of plant-generated volatile monoterpenes depend on monoterpene partitioning between air, aqueous and lipid-phases in the leaves. While Henry's law constants (H pc, equilibrium gas/water partition coefficient) and octanol/water partition coefficients (K OW) for pure water have been previously used to simulate monoterpene emissions from the leaves, aqueous phase in plants is a complex solution of electrolytes and neutral osmotica. We studied the effects of dissociated compounds KCl and glycine and sugars glucose, sorbitol and sucrose with concentrations between 0 and 1M on H pc and K OW values for limonene and linalool. Linalool with ca. 1500-fold lower H(pc) (2.62 Pa m(3)mol(-1) for pure water at 30 degrees C) and ca. 30-fold lower K OW (955 mol mol(-1) for pure water at 25 degrees C) is the more hydrophilic compound of the two monoterpenes. H pc of both monoterpenes increased with increasing concentration of both ionic compounds and sorbitol, but decreased with increasing glucose and sucrose concentrations. The salting-out coefficients for H pc (kH) were ca. an order of magnitude larger for more hydrophilic compound linalool than for more hydrophobic limonene. For linalool, co-solutes modified H pc by 30-50% at the highest concentration (1M) tested. The effect of temperature on the salting-out coefficient of KCl was minor. As with H pc, K OW increased with increasing the concentration of KCl, glycine and sorbitol, and decreased with increasing glucose and sucrose concentrations. For limonene, co-solutes modified K OW by 20-50% at the highest concentration used. For linalool, the corresponding range was 10-35%. Salting-out coefficients for H pc and K OW were correlated, but the lipid-solubility was more strongly affected than aqueous solubility in the case of limonene. Overall, these data demonstrate physiologically important effects of co-solutes on H pc and K OW for hydrophilic monoterpenes and on K OW for hydrophobic monoterpenes that should be included in current emission models.     

Temperature dependencies of Henry's law constants and octanol/water partition coefficients for key plant volatile monoterpenoids

To model the emission dynamics and changes in fractional composition of monoterpenoids from plant leaves, temperature dependencies of equilibrium coefficients must be known. Henry's law constants (H(pc), Pa m3 mol(-1) and octanol/water partition coefficients (K(OW), mol mol(-1)) were determined for 10 important plant monoterpenes at physiological temperature ranges (25-50 degrees C for H(pc) and 20-50 degrees C for K(OW)). A standard EPICS procedure was established to determine H(pc) and a shake flask method was used for the measurements of K(OW). The enthalpy of volatilization (deltaH(vol)) varied from 18.0 to 44.3 kJ mol(-1) among the monoterpenes, corresponding to a range of temperature-dependent increase in H(pc) between 1.3- and 1.8-fold per 10 degrees C rise in temperature. The enthalpy of water-octanol phase change varied from -11.0 to -23.8 kJ mol(-1), corresponding to a decrease of K(OW) between 1.15- and 1.32-fold per 10 degrees C increase in temperature. Correlations among physico-chemical characteristics of a wide range of monoterpenes were analyzed to seek the ways of derivation of H(pc) and K(OW) values from other monoterpene physico-chemical characteristics. H(pc) was strongly correlated with monoterpene saturated vapor pressure (P(v)), and for lipophilic monoterpenes, deltaH(vol) scaled positively with the enthalpy of vaporization that characterizes the temperature dependence of P(v) Thus, P(v) versus temperature relations may be employed to derive the temperature relations of H(pc) for these monoterpenes. These data collectively indicate that monoterpene differences in H(pc) and K(OW) temperature relations can importantly modify monoterpene emissions from and deposition on plant leaves.     

QSAR study on the toxicity of substituted benzenes to the algae (Scenedesmus obliquus).

50% effective inhibition concentration 48h-EC50 of 40 substituted benzenes to the algae (Scenedesmus obliquus) was determined. The energy of the lowest unoccupied molecular orbital (E(LUMO)) was calculated by the quantum chemical method MOPAC6.0-AM1. By using E(LUMO) and the hydrophobicity parameter log K(OW) the quantitative structure-activity relationship model (QSAR) was developed: log1/EC50=0.272 logK(OW) - 0.659E(LUMO) + 2.54, R2 = 0.793, S.E. = 0.316, F = 71.07, n = 40. A series of equations were obtained about the measured EC50 values of different subclasses of compounds. For those compounds containing double -NO2, their toxicity may be related chiefly to the intracellular reduction of -NO2 obtaining electron, while for anilines and phenols, K(OW) contributes most to the QSAR and E(LUMO) very little.     

A study of the partitioning behavior of Irgarol-1051 and its transformation products

Partitioning behavior of the antifouling booster biocide, Irgarol-1051 (2-methythio-4-tert-butylamino-6-cyclopropylamino-s-triazine), its production by-product, M3, and its environmental transformation products, M1 and M2, were studied. Octanol-water partition coefficients, log K(OW), and organic matter-water partition coefficients, log K(OC), of these s-triazines were measured by reversed-phase HPLC and a triphasic SPME equilibrium model, respectively. The average log K(OW) (+/-SD) of the four s-triazine species were: 4.39+/-0.07 (M3); 3.38+/-0.12 (Irgarol-1051); 2.92+/-0.12 (M2) and 2.54+/-0.11 (M1), while mean log K(OC) (+/-SD) of these species were: 2.47+/-0.03 (M3); 2.16+/-0.03 (Irgarol-1051); 1.97+/-0.03 (M2) and 1.79+/-0.04 (M1). These results were compared to reported physicochemical parameters of Irgarol-1051 in the literature. Partitioning behavior of these s-triazine species in the coastal environment revealed by their K(OW) and K(OC) were also discussed.     

Use of different organic wastes in reducing the potential leaching of propanil,isoxaben, cadusafos and pencycuron through the soil

In this study, we examined the effect of four different organic wastes (OW)—composted sheep manure (CSM), spent coffee grounds (SCG), composted pine bark (CPB) and coir (CR)—on the potential groundwater pollution of propanil and isoxaben (herbicides), cadusafos (insecticide) and pencycuron (fungicide) under laboratory conditions. For this purpose, leaching studies were conducted using disturbed soil columns filled with a clay loam soil (Hipercalcic calcisol). The addition of organic matter (OM) drastically reduced the movement of the studied pesticides. The results obtained point to the interest in the use of agro-industrial and composted OW in reducing the groundwater pollution by pesticide drainage.     

Photocatalytic demulsification of oil/water emulsions containing nonionic surfactant

Environmental Science and Pollution Research - Separation of oil-water (OW) emulsions is investigated using a photocatalytic demulsification approach. Experiments were conducted using two types of...     

Absorption of decabromodiphenyl ether and other organohalogen chemicals by grey seals (Halichoerus grypus)

An input-output balance study was performed for polybrominated diphenyl ethers, polychlorinated biphenyls and some organochlorine pesticides on three captive, juvenile grey seals (Halichoerus grypus). The animals were fed a diet of herring for six months, during the last three months of which this study was performed. A supplement of decabromodiphenyl ether was included in the diet during the second month of the study. Consistently high absorption (>89%) was observed for all of the chemicals studied, whereas work on other animals has generally shown high (>80%) net absorption at log K(OW) < approximately 6, dropping towards higher log K(OW), and very low absorption of decabromodiphenyl ether. The half-life of decabromodiphenyl ether in blood was estimated to be between 8.5 and 13 days. Measurable concentrations of decabromodiphenyl ether were detected in seal blubber at the end of the study, indicating that this chemical can be stored in adipose and may bioaccumulate. Current understanding of the mechanism of absorption of organohalogen chemicals and the potential for accumulation of decabromodiphenyl ether will need reassessing in the light of these results.     

The influence of gill and liver metabolism on the predicted bioconcentration of three pharmaceuticals in fish

The potential for xenobiotic compounds to bioconcentrate is typically expressed through the bioconcentration factor (BCF), which has gained increased regulatory significance over the past decade. Due to the expense of in vivo bioconcentration studies and the growing regulatory need to assess bioconcentration potential, BCF is often calculated via single-compartment models, using K(OW) as the primary input. Recent efforts to refine BCF models have focused on physiological factors, including the ability of the organism to eliminate the compound through metabolic transformation. This study looks at the ability of in vitro biotransformation assays using S9 fractions to provide an indication of metabolic potential. Given the importance of the fish gill and liver in metabolic transformation, the metabolic loss of ibuprofen, norethindrone and propranolol was measured using rainbow trout (Oncorhynchus mykiss) and channel catfish (Ictalurus punctatus) gill and liver S9 fractions. Metabolic transformation rates (k(M)) were calculated and integrated into a refined BCF model. A significant difference was noted between BCF solely based on K(OW) and BCF including k(M). These studies indicate that the inclusion of k(M) in BCF models can bring predicted bioconcentration estimates closer to in vivo values.     

Physiological and growth responses of differentially irrigated cotton to ozone

This study was conducted to determine the physiological and growth responses of cotton (Gossypium hirsutum L.) to the interaction of ozonee (O3) and drought stress. Cotton (cv SJ-2) was grown in open-top chambers in the field at three levels of soil water and exposed to charcoal-filtered air (CF), nonfiltered air (NF), and NF x 1.25, and NF x 1.5 ambient O3 concentrations in Riverside, CA, from June to October 1986. Ozone reduced carbon fixation an average of 74.6% in optimally watered (OW) plots, 63.4% in suboptimal (SO) plots, but only 19.3% in severely water-stressed (SS) plots. Leaf and stem biomass in OW and SO plots showed similar linear reductions in mass response to increased O3 concentrations, but SS plots showed no response to O3 except at the highest O3 treatment (seasonal 12-h O3 mean of 0.111 ppm 218 microm(-3)). These results showed that moderately water-stressed cotton had similar physiological and growth responses to O3 as well-watered plants, but severely water-stressed cotton showed little response to O3 at ambient O3 concentrations.     

Quantitative structure-activity relationships of nitroaromatics toxicity to the algae (Scenedesmus obliguus)

The DFT-B3LYP method, with the basis set 6-311G( * *), was employed to calculate the molecular geometries and electronic structures of 25 nitroaromatics. The acute toxicity (-lgEC(50)) of these compounds to the algae (Scenedesmus obliguus) along with hydrophobicity described by logK(OW), and two quantum chemical parameters-energy of the lowest unoccupied molecular orbital, E(LUMO), and the charge of the nitro group, [ForQ(NO2), were used to establish the quantitative structure-activity relationships (QSARs). For 18 mononitro derivatives, the hydrophobicity parameter logK(OW) could interpret the toxic mechanism successfully. Dinitro aromatic compounds were susceptible to be reduced to aniline for their electrophilic nature. Their toxicity was controlled mainly by electronic factors instead of hydrophobicity. The electronic parameters, E(LUMO) and Q(NO2), were used to yield the following model: -lg EC(50) = 3.746 - 25.053 E(LUMO) + 6.481 Q(NO2) (n=22, R=0.926, SE=0.206, F=56.854, P<0.001). The predicted toxic values using the above equation are in good agreement with the experimental values.     

Calculation of environmental concentration and comparison of output for existing chemicals using regional multimedia modeling

The environmental fate of 40 existing chemicals is discussed using the EUSES multimedia distribution and risk assessment model with site-specific parameter setting in an urban area of Japan including a highly industrial region. There has been a strong need to assess the environmental fate of a huge number of existing chemicals. Data on the emission amounts of chemicals are essential for such prediction, and PRTR surveys may yield this data. The study delivered the following results: (1) Volatile compounds with large amounts of emission showed higher predicted concentrations in air, and the concentrations of several compounds agreed well with averaged monitoring data within an order of magnitude. (2) A close relationship was found between the concentration of water and that of sediment, suggesting that the fate of chemicals in sediment essentially depended on the water environment. (3) A group of volatile solvents had high mass distribution ratio to air. Some compounds having high solubility in water were also included in that group due to the high ratio of air emission. Highly hydrophobic compounds with logK(OW) larger than 6.0 showed a high distribution ratio to soil and sediment. (4) Volatile compounds were mostly taken through air. The exposure through fish is a dominant pathway for highly hydrophobic compounds. (5) Exposure ratio could be gathered from physicochemical properties. The exposure from fish intake was roughly estimated by logK(OW), whereas exposure from air and water intake was difficult to estimate simply by vapor pressure and solubility in water, respectively.     

Investigations on the sorption of phenols to dissolved organic matter by a QSAR study

The sorption of various phenols to Aldrich-HA and BSA was investigated by solid phase microextraction (SPME). The Aldrich-HA sorption with log K(DOC)-values between 2 and 3 was determined, whereas the sorption to BSA with log K(DOC)-values between 2 and 6 was much stronger. To enable an estimation of sorption constants a QSAR model was investigated. The linear free energy relationship (LFER) model showed a good correlation between the sorption constants and the log K(OW)-values with correlation coefficients of R = 0.910 and R = 0.878 for Aldrich-HA and BSA, respectively.