Leaching of S-metolachlor,terbuthylazine, desethyl-terbuthylazine,mesotrione, flufenacet,isoxaflutole, and diketonitrile in field lysimeters as affected by the time elapsed between spraying and first leaching event

The effect of elapsed time between spraying and first leaching event on the leaching behavior of five herbicides (terbuthylazine, S-metolachlor, mesotrione, flufenacet, and isoxaflutole) and two metabolites (desethyl-terbuthylazine and diketonitrile) was evaluated in a 2011–2012 study in northwest Italy. A battery of 12 lysimeters (8.4 m² long with a depth of 1.8 m) were used in the study, each filled with silty-loam soil and treated during pre-emergence with the selected herbicides by applying a mixture of commercial products Lumax (4 L ha^?1) and Merlin Gold (1 L ha^?1). During treatment periods, no gravity water was present in lysimeters. Irrigation events capable of producing leaching (40 mm) were conducted on independent groups of three lysimeters on 1 day after treatment (1 DAT), 7 DAT, 14 DAT, and 28 DAT. The series was then repeated 14 days later. Leachate samples were collected a few days after irrigation; compounds were extracted by solid phase extraction and analyzed by high-performance liquid chromatography and gas chromatography–mass spectrometry. Under study conditions, terbuthylazine and S-metolachlor showed the highest leaching potentials. Specifically, S-metolachlor concentrations were always found above 0.25 µg L^?1. Desethyl-terbuthylazine was often detected in leached waters, in most cases at concentrations above 0.1 µg L^?1. Flufenacet leached only when irrigation occurred close to the time of herbicide spraying. Isoxaflutole and mesotrione were not measured (<0.1 µg L^?1), while diketonitrile was detected in concentrations above 0.1 µg L^?1 on 1 DAT in 2011 only.     

Acute toxicity of chlorpyrifos to embryo and larvae of banded gourami Trichogaster fasciata

This study elucidated the acute toxicity of chlorpyrifos on the early life stages of banded gourami (Trichogaster fasciata). To determine the acute effects of chlorpyrifos on their survival and development, we exposedthe embryos and two-day-old larvae to six concentrations (0, 0.01, 0.10, 1.0, 10 and 100 µg L^?1) of chlorpyrifos in plastic bowls. Log-logistic regression was used to calculate LC10 and LC50 values. Results showed that embryo mortality significantly increased with increasing chlorpyrifos concentrations. The 24-h LC10 and LC50 values (with 95% confidence limits) of chlorpyrifos for embryos were 0.89 (0.50–1.58) and 11.8 (9.12–15.4) µg L^?1, respectively. Hatching success decreased and mortality of larvae significantly increased with increasing concentrations of chlorpyrifos. The 24-h LC10 and LC50 values (with 95% confidence limits) of chlorpyrifos for larvae were 0.53 (0.27–1.06) and 21.7 (15.9–29.4) µg L^?1, respectively; the 48-h LC10 and LC50 for larvae were 0.04 (0.02–0.09) and 5.47 (3.77–7.94) µg L^?1, respectively. The results of this study suggest that 1 µg L^?1 of chlorpyrifos in the aquatic environment may adversely affect the development and the reproduction of banded gourami. Our study also suggests that banded gourami fish can serve as an ideal model species for evaluating developmental toxicity of environmental contaminants.     

Chicken manure enhanced yield and quality of field-grown kale and collard greens

Organic matter and nutrients in municipal sewage sludge (SS) and chicken manure (CM) could be recycled and used for land farming to enhance fertility and physical properties of soils. Three soil management practices were used at Kentucky State University Research Farm, Franklin County, to study the impact of soil amendments on kale (Brassica oleracea cv. Winterbar) and collard (Brassica oleracea cv. Top Bunch) yields and quality. The three soil management practices were: (i) SS mixed with native soil at 15 t acre^?1, (ii) CM mixed with native soil at 15 t acre^?1, and (iii) no-mulch (NM) native soil for comparison purposes. At harvest, collard and kale green plants were graded according to USDA standards. Plants grown in CM and SS amended soil produced the greatest number of U.S. No. 1 grade of collard and kale greens compared to NM native soil. Across all treatments, concentrations of ascorbic acid and phenols were generally greater in kale than in collards. Overall, CM and SS enhanced total phenols and ascorbic acid contents of kale and collard compared to NM native soil. We investigated the chemical and physical properties of each of the three soil treatments that might explain variability among treatments and the impact of soil amendments on yield, phenols, and ascorbic acid contents of kale and collard green grown under this practice.     

Advances in the Analysis of Air Contaminants Comments

Abstract

Methylcyclopentadienyl manganese tricarbonyl (MMT) is an organometallic compound used as an octane improver in unleaded gasoline. The combustion of MMT leads to the formation of manganese (Mn) oxides, mainly Mn₃O₄. The objective of this study is to assess the variations over time and space of respirable (Mn_R) and total (Mn_T) Mn in the urban atmosphere and to evaluate human exposure by inhalation. Two sampling sites were selected on the island of Montreal based on their local traffic density (municipal botanical garden, C^-= 10,000–15,000 vehicles d^-1; Montreal Waterworks, C⁺= 100,000–130,000 vehicles d^-1). Air samplings were made during the day at stations located 10 m from the road using portable pumps, some of which were equipped with a cyclone. Mn_R and Mn_T and other metals were measured on Teflon filters by neutron activation. Mn exposure doses by inhalation were calculated using Monte–Carlo simulations. Mn_R and Mn_T average concentrations were significantly higher at site C⁺ (Mn_R = 0.024 µg m^-3; Mn_T = 0.050 µg m^-3) than at site C^- (Mn_R= 0.015 µg m^-3; Mn_T= 0.027 µg m^-3). Temporal profiles at sites C⁺ and site C^-were similar, with a coefficient of correlation of 0.24 for Mn_R and 0.26 for Mn_T. Trend analyses (ARIMA) also showed that the period of the week (work days vs. off days) was significantly related to Mn_R and Mn_T variations at both sites. The average exposure dose by inhalation to Mn_R and Mn_T ranged from 0.001 to 0.030 µg kg^-1 day^-1 and 0.001 to 0.05 µg kg^-1 day^-1. Mn_R and Mn_T concentrations reflected a positive relationship with traffic density. However, it remains difficult to attribute these results directly to the combustion of MMT in unleaded gasoline. On average, the Mn_R and Mn_T inhalation doses were 2 to 15 times lower than the reference dose (RfC) proposed by the U.S. Environmental Protection Agency (EPA) for the general population.     

Recent spatial gradients and time trends in Dhaka,Bangladesh, air pollution and their human health implications

Dhaka, the capital of Bangladesh, is among the most polluted cities in the world. This research evaluates seasonal patterns, day-of-week patterns, spatial gradients, and trends in PM_2.5 (<2.5 µm in aerodynamic diameter), PM₁₀ (<10 µm in aerodynamic diameter), and gaseous pollutants concentrations (SO₂, NO₂, CO, and O₃) monitored in Dhaka from 2013 to 2017. It expands on past work by considering multiple monitoring sites and air pollutants. Except for ozone, the average concentrations of these pollutants showed strong seasonal variation, with maximum during winter and minimum during monsoon, with the pollution concentration of PM_2.5 and PM₁₀ being roughly five- to sixfold higher during winter versus monsoon. Our comparisons of the pollutant concentrations with Bangladesh NAAQS and U.S. NAAQS limits analysis indicate particulate matter (PM_2.5 and PM₁₀) as the air pollutants of greatest concern, as they frequently exceeded the Bangladesh NAAQS and U.S. NAAQS, especially during nonmonsoon time. In contrast, gaseous pollutants reported far fewer exceedances throughout the study period. During the study period, the highest number of exceedances of NAAQS limits in Dhaka City (Darus-Salam site) were found for PM_2.5 (72% of total study days), followed by PM₁₀ (40% of total study days), O₃ (1.7% of total study days), SO₂ (0.38% of total study days), and CO (0.25% of total study days). The trend analyses results showed statistically significant positive slopes over time for SO₂ (5.6 ppb yr^?1, 95% confidence interval [CI]: 0.7, 10.5) and CO (0.32 ppm yr^?1, 95% CI: 0.01, 0.56), which suggest increase in brick kilns operation and high-sulfur diesel use. Though statistically nonsignificant annual decreasing slopes for PM_2.5 (?4.6 µg/m³ yr^?1, 95% CI: ?12.7, 3.6) and PM₁₀ (?2.7 µg/m³ yr^?1, 95% CI: ?7.9, 2.5) were observed during this study period, the PM_2.5 concentration is still too high (~ 82.0 µg/m³) and can cause severe impact on human health.

Implications: This study revealed key insights into air quality challenges across Dhaka, Bangladesh, indicating particulate matter (PM) as Dhaka’s most serious air pollutant threat to human health. The results of these analyses indicate that there is a need for immediate further investigations, and action based on those investigations, including the conduct local epidemiological PM exposure-human health effects studies for this city, in order to determine the most public health effective interventions.     

Degradation of chlorpyrifos and its hydrolysis product, 3,5,6‐trichloro‐2‐pyridinol,in soil

Abstract

The degradation of ¹⁴C‐chlorpyrifos and its hydrolysis product, 3,5,6‐trichloro‐2‐pyridinol (TCP), was investigated in soil in laboratory experiments. Between 12 and 57% of the applied chlorpyrifos persisted in a variety of agricultural soils after a 4‐week incubation. Concentrations of TCP present in these soils ranged from 1 to 34% of the applied dose. Two patterns of persistence were observed. In some soils, significant quantities of TCP and soil‐bound residues were produced, but little ¹⁴CO₂. In other soils, neither TCP nor soil‐bound residues accumulated, but large quantities of ¹⁴CO₂ were evolved. Direct treatment of fresh samples of each of these soils with ¹⁴C‐TCP resulted in rapid mineralization of TCP to ¹⁴CO₂ only in those soils in which TCP had not accumulated after chlorpyrifos treatment. The rapid mineralization of TCP in these soils was microbially mediated, but populations of soil microorganisms capable of using TCP as a sole carbon‐energy source were not detected.     

Analysis and fate of acephate and its metabolite,methamidophos, in pepper and cucumber

Abstract

Levels of acephate (Orthene^R) and its principle metabolite, methamidophos, in/on greenhouse‐grown pepper and cucumber fruits and leaves in relation to the applied methamidophos were monitored. Dislodgeable and total residues of acephate and methamidophos were determined by gas‐liquid chromatography equipped with a flame ionization detector (GC‐FID) and were confirmed by nitrogen phosphorus detector (GC‐NPD). The dissipation curves of the residues followed first‐order kinetics (R²> 0.96). Initial residues of acephate on fruits varied between pepper (15.12 ppm) and cucumber (2.16 ppm) . Total residues in fruits and leaves determined at intervals following application revealed the greater persistence of acephate on pepper fruits (half‐life [t_1/2] of 6 d) than on cucumber fruits (t_1/2 was 3.7 d) . T_1/2 values for the applied methamidophos were 4.7 and 5.3 d on pepper and cucumber fruits, respectively. Deacety‐lation of acephate (formation of its metabolite) was detectable 1 d following acephate treatment and reached a maximum of 2.05% of initial acephate residues 3 d after application on pepper fruits. On cucumber fruits, acephate metabolite reached a maximum of 2.12% one wk following application. No acephate residues were detected above the limit of detection of 0.001 ppm in pepper fruits 50 d following acephate application while its metabolite was detectable at that time (detectability limit was 0.0001 ppm).     

Method Development for Determination of Fluroxypyr in Soil

Abstract

Four methods were developed for the analysis of fluroxypyr in soil samples from oil palm plantations. The first method involved the extraction of the herbicide with 0.05 M NaOH in methanol followed by purification using acid base partition. The concentrated material was subjected to derivatization and then cleaning process using a florisil column and finally analyzed by gas chromatography (GC) equipped with electron capture detector (ECD). By this method, the recovery of fluroxypyr from the spiked soil ranged from 70 to 104% with the minimum detection limit at 5 µg/kg. The second method involved solid liquid extraction of fluroxypyr using a horizontal shaker followed by quantification using high performance liquid chromatography (HPLC) equipped with UV detector. The recovery of fluroxypyr using this method, ranged from 80 to 120% when the soil was spiked with fluroxypyr at 0.1–0.2 µg/g soil. In the third method, the recovery of fluroxypyr was determined by solid liquid extraction using an ultrasonic bath. The recovery of fluroxypyr at spiking levels of 4–50 µg/L ranged from 88 to 98% with relative standard deviations of 3.0–5.8% with a minimum detection limit of 4 µg/kg. In the fourth method, fluroxypyr was extracted using the solid liquid extraction method followed by the cleaning up step with OASIS® HLB (polyvinyl dibenzene). The recovery of fluroxypyr was between 91 and 95% with relative standard deviations of 4.2–6.2%, respectively. The limit of detection in method 4 was further improved to 1 µg/kg. When the weight of soil used was increased 4 fold, the recovery of fluroxypyr at spiking level of 1–50 µg/kg ranged from 82–107% with relative standard deviations of 0.5–4.7%.     

Repeated batch and continuous degradation of chlorpyrifos by Pseudomonas putida

The present study was undertaken with the objective of studying repeated batch and continuous degradation of chlorpyrifos (O,O-diethyl O-3,5,6-trichloropyridin-2-yl phosphorothioate) using Ca-alginate immobilized cells of Pseudomonas putida isolated from an agricultural soil, and to study the genes and enzymes involved in degradation. The study was carried out to reduce the toxicity of chlorpyrifos by degrading it to less toxic metabolites. Long-term stability of pesticide degradation was studied during repeated batch degradation of chlorpyrifos, which was carried out over a period of 50 days. Immobilized cells were able to show 65% degradation of chlorpyrifos at the end of the 50th cycle with a cell leakage of 112 × 10³ cfu mL^?1. During continuous treatment, 100% degradation was observed at 100 mL h^?1 flow rate with 2% chlorpyrifos, and with 10% concentration of chlorpyrifos 98% and 80% degradation was recorded at 20 mL h^?1 and 100 mL h^?1 flow rate respectively. The products of degradation detected by liquid chromatography–mass spectrometry analysis were 3,5,6-trichloro-2-pyridinol and chlorpyrifos oxon. Plasmid curing experiments with ethidium bromide indicated that genes responsible for the degradation of chlorpyrifos are present on the chromosome and not on the plasmid. The results of Polymerase chain reaction indicate that a ~890-bp product expected for mpd gene was present in Ps. putida. Enzymatic degradation studies indicated that the enzymes involved in the degradation of chlorpyrifos are membrane-bound. The study indicates that immobilized cells of Ps. putida have the potential to be used in bioremediation of water contaminated with chlorpyrifos.     

Rapid and Sensitive LC/MS/MS Direct Injection Method for the Determination of Trace Level Corexit EC9500A Oil Dispersant in Seawater

A rapid and sensitive liquid chromatography tandem mass spectrometry (LC/MS/MS) method for the determination of trace dioctyl sulfosuccinate (DOSS) concentrations in seawater samples has been established. The method is well suited to aquatic environment impact monitoring following application of the dispersant Corexit EC9500A. Linearity of the method was demonstrated down to 0.05 ng/mL^?1 (0.05 µgL^?1) DOSS in seawater, with a 2.4% relative standard deviation precision for preparation replicates. A US EPA method limit of detection of <0.02 ng/mL^?1 (<0.02 µgL^?1) was calculated and specificity was confirmed by monitoring of two qualifier ions at 291.1 m/z and 227.1 m/z. These transitions were confirmed by QToF analysis to be associated with the DOSS precursor ion at 421.2 m/z. For application to seawater samples and samples containing oil particulates, a practical and repeatable calibration range of 0.5 ng/mL^?1 (0.5 µgL^?1) to 25.0 ng/mL^?1 (25.0 µgL^?1) DOSS is reported. The method was shown to have excellent precision and accuracy, with a consistent ≤1.6% relative standard deviation for system suitability standards at 0.5 ng/mL^?1 (0.5 µgL^?1) and linear weighted (1/x) regression coefficients of determination ≥0.995. The surfactant nature of the analyte is discussed in relation to detection limit and loss of analyte. Speculation of a relationship between DOSS in association or aggregation with divalent cations, such as Ca²⁺ present in salt water and hard water, is suggested. The consequent effects on cell ionic balance and membrane function are discussed.     

Dissipation,half-lives,and mass spectrometric identification of endosulfan isomers and the sulfate metabolite on three field-grown vegetables

Endosulfan 3 EC, a mixture of α- and β-stereo isomers, was sprayed on field-grown pepper, melon, and sweet potato plants at the recommended rate of 0.44 kg A.I. acre^?1. Plant tissue samples (leaves, fruits, or edible roots) were collected 1 h to 30 days following spraying and analyzed for endosulfan isomers (α- and β-isomers). Analysis of samples was accomplished using a gas chromatograph (GC) equipped with a mass detector in total ion mode. The results indicated the formation of endosulfan sulfate as the major metabolite of endosulfan sulfite and the relatively higher persistence of the β-isomers as compared to the α-isomer. The initial total residues (α- and β-isomers plus endosulfan sulfate) were higher on leaves than on fruits. On pepper and melon fruits, the α-isomer, which is the more toxic to mammals, dissipated faster (T_1/2 = 1.22 and 0.95 d, respectively) than the less toxic β-isomer (T_1/2 = 3.0 and 2.5 d, respectively). These results confirm the greater loss of the α-isomer compared to the β-isomer, which can ultimately impact endosulfan dissipation in the environment. Additionally, the higher initial residues of endosulfan on pepper and sweet potato leaves should be considered of great importance for timing field operations and the safe entry of harvesters due to the high mammalian toxicity of endosulfan.     

Comparative sorption,desorption and leaching potential of aminocyclopyrachlor and picloram

Sorption and desorption of aminocyclopyrachlor (6-amino-5-chloro-2-cyclopropylpyrimidine-4-carboxylic acid) were compared to that of the structurally similar herbicide picloram (4-amino-3,5,6-trichloro-2-pyridinecarboxylic acid) in three soils of differing origin and composition to determine if picloram data is representative of aminocyclopyrachlor behavior in soil. Aminocyclopyrachlor and picloram batch sorption data fit the Freundlich equation and was independent of concentration for aminocyclopyrachlor (1/n = 1), but not for picloram (1/n = 0.80–0.90). Freundlich sorption coefficients (K _f) for aminocyclopyrachlor were lowest in the eroded and depositional Minnesota soils (0.04 and 0.12 μmol ^(1–1/n) L^1/n kg^?1) and the highest in Molokai soil (0.31 μmol ^(1–1/n) L^1/n kg^?1). For picloram, K _f was lower in the eroded (0.28 μmol ^(1–1/n) L^1/n kg^?1) as compared to the depositional Minnesota soil (0.75 μmol ^(1–1/n) L^1/n kg^?1). Comparing soil to soil, K _f for picloram was consistently higher than those found for aminocyclopyrachlor. Desorption of aminocyclopyrachlor and picloram was hysteretic on all three soils. With regard to the theoretical leaching potential based on groundwater ubiquity score (GUS), leaching potential of both herbicides was considered to be similar. Aminocyclopyrachlor would be ranked as leacher in all three soils if t_1/2 was > 12.7 days. To be ranked as non-leacher in all three soils, aminocyclopyrachlor t_1/2 would have to be <3.3 days. Calculated half-life that would rank picloram as leacher was calculated to be ～15.6 d. Using the current information for aminocycloprachlor, or using picloram data as representative of aminocycloprachlor behavior, scientists can now more accurately predict the potential for offsite transport of aminocycloprachlor.     

Short chain nitrocompounds as a treatment of layer hen manure and litter; effects on in vitro survivability of Salmonella,generic E. coli and nitrogen metabolism

The current study was conducted to assess the bactericidal effectiveness of several nitrocompounds against pathogens in layer hen manure and litter. Evidence from an initial study indicated that treatment of layer hen manure with 12 mM nitroethane decreased populations of generic E. coli and total coliforms by 0.7 and 2.2 log₁₀ colony forming units (CFU) g^?1, respectively, after 24 h aerobic incubation at ambient temperature when compared to untreated populations. Salmonella concentrations were unaffected by nitroethane in this study. In a follow-up experiment, treatment of 6-month-old layer hen litter (mixed with 0.4 mL water g^?1) with 44 mM 2-nitroethanol, 2-nitropropanol or ethyl nitroacetate decreased an inoculated Salmonella typhimurium strain from its initial concentration (3 log₁₀ CFU g^?1) by 0.7 to 1.7 log₁₀ CFU g^?1 after 6 h incubation at 37°C in covered containers. After 24 h incubation, populations of the inoculated S. Typhmiurium in litter treated with 44 mM 2-nitroethanol, 2-nitropropanol, ethyl nitroacetate or nitroethane were decreased more than 3.2 log₁₀ CFU g^?1 compared to populations in untreated control litter. Treatment of litter with 44 mM 2-nitroethanol, 2-nitropropanol, ethyl nitroacetate decreased rates of ammonia accumulation more than 70% compared to untreated controls (0.167 µmol mL^?1 h^?1) and loses of uric acid (< 1 µmol mL^?1) were observed only in litter treated with 44 mM 2-nitropropanol, indicating that some of these nitrocompounds may help prevent loss of nitrogen in treated litter. Results warrant further research to determine if these nitrocompounds can be developed into an environmentally sustainable and safe strategy to eliminate pathogens from poultry litter, while preserving its nitrogen content as a nutritionally valuable crude protein source for ruminants.     

Stability of cocaine and its metabolites in municipal wastewater – the case for using metabolite consolidation to monitor cocaine utilization

Transformations of cocaine and eleven of its metabolites were investigated in untreated municipal sewage at pH?≈?7 and 9, 23, and 31 °C. Results indicated that hydrolysis—possibly bacterially mediated—was the principal transformation pathway. Residues possessing alkyl esters were particularly susceptible to hydrolysis, with pseudo-first-order rate constants varying from 0.54 to 1.7 day^?1 at 23 °C. Metabolites lacking esters or possessing only a benzoyl ester appeared stable. Residues lacking alkyl esters did accumulate through hydrolysis of precursors, however. As noted previously, this may positively bias cocaine utilization estimates based on benzoylecgonine alone. Reported variability in metabolic excretion was used in conjunction with transformation data to evaluate different approaches for estimating cocaine loading. Results indicate that estimates derived from measurands that capture all major cocaine metabolites, such as COC_tot (the sum of all measurable metabolites) and EC_hyd (the sum of all metabolites that can be hydrolyzed to ecgonine), may reduce uncertainty arising from variability in metabolite transformation and excretion, possibly to?≈?10 % RSD. This is more than a two-fold reduction relative to estimates derived from benzoylecgonine (>26 % RSD), and roughly equivalent to reported uncertainties from sources that are not metabolite-specific (e.g., sampling frequency, flow variability). They and other composite measurands merit consideration from the sewage epidemiology community, beginning with efforts to evaluate the stability of the total cocaine load under realistic sewer conditions.     

Glucosinolates in collard greens grown under three soil management practices

Glucosinolates (GSLs, β-D-thioglucoside-N-hydroxysulfates) are polar compounds present in varying amounts in members of the Brassicaceae family. They suppress soil-borne pests due to the biofumigant properties of the highly toxic isothiocyanates present in Brassica vegetables. The objectives of this investigation were to: (1) assess variation in GSLs concentrations among collard plants grown under three soil management practices: sewage sludge (SS) mixed with native soil, chicken manure (CM) mixed with native soil, and no-mulch (NM) native soil, (2) quantify GSLs concentrations in collard roots, leaves, and stems at harvest for potential use of their crude extracts in plant protection, and (3) assess myrosinase activity in soil amended with CM and SS mixed with native soil. Separation of GSLs was accomplished by adsorption on a DEAE-Sephadex ion exchange resin using disposable pipette tips filled with DEAE, a weak base, with a net positive charge when ionized and exchange anions such as GSLs (hydrophilic plant secondary metabolites). Quantification of total GSLs was based on inactivation of collard endogenous myrosinase and liberation of the glucose moiety from the GSLs molecule by addition of standardized myrosinase and colorimetric determination of the liberated glucose moiety. Across all treatments, SS and CM increased soil organic matter content from 2.2% in native soil to 4.2 and 6.5%, respectively. GSLs concentrations were significantly greater in collard leaves (30.9 µmoles g^?1 fresh weight) compared to roots and stems (7.8 and 1.2 µmoles g^?1 fresh weight), respectively. Leaves of collard grown in soil amended with SS contained the greatest concentrations of GSLs compared to leaves of plants grown in CM and NM treatments. Accordingly, leaves of collard plants grown in soil amended with SS could play a significant role in sustainable agriculture as alternative tools for soil-borne disease management in conventional and organic agriculture.     

Reference values for acetyl and butyrylcholinesterases in cattle under actual management conditions,hepatic and renal function by application of chlorpyrifos

Chlorpyrifos is an anticholinesterase organophosphate insecticide widely used in Argentina in the production of food derived from animal, fruit and horticultural origin and is reported as a residue within these products. Local reference values for acetyl and butyrylcholinesterase were determined in Aberdeen Angus bovine and cross bred cattle (n = 25), a requirement to be able to evaluate toxicity of commercial organophosphate and carbamate formulations. The activity of cholinesterase enzymes presented an overall mean of 2,183.00 ± 485.6 IU L^?1 for erythrocyte acetylcholinesterase and 203.1 ± 42.06 IU L^?1 for plasma butyrylcholinesterase, which are used as reference values for meat steers within a system of intensive production in a semi-arid region. The toxic potential of chlorpyrifos in steers of the same breeds (n = 12) was assessed applying chlorpyrifos 15.00% Tipertox® in a single therapeutic dose of 7.50 mg kg^?1 by topical route. Prior to application and then on day 1 and day 21 post-application, both blood cholinesterases, serum chlorpyrifos concentration by ultra-high resolution liquid chromatography with mass detector, analysis of blood counts, total proteins, liver enzymes, urea and creatinine were evaluated. The mean plasma concentration of chlorpyrifos was 27.90 ug L^?1 at 24 h. The findings indicate that the therapeutic treatment of castrated male bovines treated with chlorpyrifos, applied by pour-on according to the manufacturer's instructions, does not cause changes in the variables evaluated.     

Biodegradation of α and β Endosulfan in Soil as Influenced by Application of Different Organic Materials

Abstract

A laboratory pot experiment was conducted to study the effect of amending soil with four different sources of organic matter on the degradation rate of α and β endosulfan isomers. Poultry by-product meal, poultry manure, dairy manure, and municipal solid waste compost were cured, dried, ground (<1 mm) and thoroughly mixed with a calcareous soil at a rate of 2% and placed in plastic pots. Endosulfan was added at the rate of 20 mg kg^?1. The moisture level was kept near field capacity and the pots were kept at room temperature. Soil sub-samples, 100 g each, were collected from every pot at days 1, 8, 15, 22, 29, 43, and 57 for the measurement of endosulfan isomers. Endosulfan residues were extracted from the soil samples with acetone. The supernatant was filtered through anhydrous sodium sulphate, 5 mL aliquot was diluted to 25 mL with hexane, mixed well, and then two sub-samples from the filtrates were analyzed for α and β endosulfan isomers by gas chromatography. The results indicated that the half-life (T _½) of α-endosulfan in the poultry by-product meal treatment was 15 days compared to about 22 days in the other treatments. The T _½ of β-endosulfan was 22 days in the poultry by-product meal treatment and followed a bi-phasic pattern, 57 days in the municipal solid waste compost treatment and the extrapolated T _½ was about 115 days for the other three treatments.     

Longterm effects of the herbicides Atrazine and Dichlobenil upon the phytoplankton density and physico-chemical conditions in compartments of a freshwater pond

Atrazine (1.1 mg · L^?1) and Dichlobenil (“DBN”) (4.3 mg · L^?1) were dosed in triplicates into the water of a compartimentalized pond. Maximum concentrations of the chemicals detected were 200 μg · L^?1 Atrazine and 4.2 mg · L^?1 DBN (on day 3 – 5 after dosing). Residues were monitored for 55 days, amounting to 60 μg Atrazine and 1.5 mg DBN per litre at the end of observation.O₂- and H⁺-concentrations were significantly lower for 35 and 30 days resp. in the treated water as compared to controls. The conductivity of the dosed water was significantly higher for at least 65 (DBN) and 120 days (Atrazine) than in the untreated compartments. Differences in phytoplankton abundance and diversity could be evaluated between controls and treated biotopes.     

Single and combined effects of aluminum (Al<Subscript>2</Subscript>O<Subscript>3</Subscript>) and zinc (ZnO) oxide nanoparticles in a freshwater fish, <Emphasis Type="Italic">Carassius auratus</Emphasis>

The increasing use of nanoparticles (NPs) worldwide has raised some concerns about their impact on the environment. The aim of the study was to assess the toxicity of metal oxide nanoparticles, singly or combined, in a freshwater fish (Carassius auratus). The fish were exposed for 7, 14, and 21 days to different concentrations of NPs (10 μg Al₂O₃.L^?1, 10 μg ZnO.L^?1, 10 μg Al₂O₃.L^?1 plus 10 μg ZnO.L^?1, 100 μg Al₂O₃.L^?1, 100 μg ZnO.L^?1, and 100 μg Al₂O₃.L^?1 plus 100 μg ZnO.L^?1). At the end of each exposure period, antioxidant enzyme activity (catalase, glutathione-S-transferase, and superoxide dismutase), lipid peroxidation, and histopathology were assessed in the gills and livers of C. auratus. The results show an increase in catalase (CAT) and superoxide dismutase (SOD) activity in the gills and livers of fish, especially after 14 days of exposure to single and combined NPs, followed by a reduction at 21 days. An increase in glutathione S-transferase (GST) was observed in gills after 7 days for all tested NP concentrations (single and combined); while in livers, a significant increase was determined after 14 days of exposure to 100 μg.L^?1 of both single ZnO and Al₂O₃ NPs. Lipid peroxidation (LPO) significantly increased in gills after 7 days of exposure to 100 μg.L^?1 Al₂O₃ NPs (single or combined). In livers, LPO increased significantly after 7 days of exposure to all tested concentrations of both single ZnO and Al₂O₃ (except for 10 μg Al₂O₃.L^?1), and after 14 days of exposure to ZnO (10 and 100 μg.L^?1) and Al₂O₃ (100 μg.L^?1)_. The results from histological observations suggest that exposure to metal oxide NPs affected both livers and gills, presenting alterations such as gill hyperplasia and liver degeneration. However, the most pronounced effects were found in gills. In general, this study shows that the tested NPs, single or combined, are capable of causing sub-lethal effects on C. auratus, but when combined, NPs seem to be slightly more toxic than when added alone.     

Degradation kinetics of tebufenozide in model aquatic systems under controlled laboratory conditions

Abstract

The hydrolysis of the insecticide tebufenozide was studied in the dark at 20 to 40°C in buffered (pH 4 to 10) distilled water, and at 20°C in unbuffered, sterilized and unsterilized stream water. Tebufenozide was very stable in acidic and neutral buffers at 20°C and the corresponding pseudo‐first‐order rate constants (k_obsd) and half‐lives (T_1/2) were 5.946 × 10^‐4 and 13.10 × 10^‐4 d^‐1, and 1166 and 529 d, respectively. The hydrolytic degradation was dependent on pH and temperature. At pH 10 and at 20,30 and 40°C, the k_obsd (10^‐4 d^‐1) and T_1/2 (d) values were 34.22, 66.72 and 130.0; and 203, 104 and 53.3, respectively. The energy of activation (E_a) values for the hydrolysis of tebufenozide at pH 4, 7 and 10, calculated from the Arrhenius plots, were 83.50, 66.71 and 50.87 kJ/mol, respectively. Tebufenozide was stable in sterilized stream water in the dark (T_1/2 = 734 d) but it degraded fairly rapidly in unsterilized stream water (T_1/2 = 181 d). Sunlight photodegradation of the chemical was slower (T_1/2 = 83.0 h) than the photolysis by ultraviolet radiations (T_1/2 values at 254 and 365 nm were 9.92 and 27.6 h, respectively); nevertheless, it was still appreciable during the summer months at 46°31’ N latitude. The differences in degradation rates between the unsterilized and sterilized stream water and the degradation of the chemical in the sterile, distilled water in sunlight, suggests that microbial processes and photolysis are the two main degradative routes for tebufenozide in natural aquatic systems.