Development and application of LC–APCI–MS method for biomonitoring of animal and human exposure to imidacloprid

Imidacloprid (IMI) is a relatively new neuro-active neonicotinoid insecticide and nowadays one of the largest selling insecticides worldwide. In the present study a LC–APCI–MS based method was developed and validated for the quantification of imidacloprid and its main metabolite 6-chloronicotinic acid (6-CINA) in urine and hair specimens. The method was tested in biomonitoring of intentionally exposed animals and subsequently applied for biomonitoring of Cretan urban and rural population.     

Earthworm ecotoxicological assessments of pesticides used to treat seeds under tropical conditions

Ecotoxicological laboratory tests (lower-tier tests) are fundamental tools for assessing the toxicity of pesticides to soil organisms. In this study, using these tests under tropical conditions, we quantified the impact of the insecticides imidacloprid, fipronil, and thiametoxam, and the fungicides captan and carboxin + thiram, all of which are used in the chemical treatment of crop seeds, on the survival, reproduction, and behavior of Eisenia andrei (Oligochaeta). With the exception of imidacloprid, none of the pesticides tested caused mortality in E. andrei in artificial soils. The LC₅₀ of imidacloprid was estimated as 25.53 mg active ingredient kg^?1 of dry soil. Earthworm reproduction rates were reduced by imidacloprid (EC₅₀ = 4.07 mg kg^?1), fipronil (EC₂₀ = 23.16 mg kg^?1), carboxin + thiram (EC₅₀ = 56.38 mg kg^?1), captan (EC₅₀ = 334.84 mg kg^?1), and thiametoxam (EC₅₀ = 791.99 mg kg^?1). Avoidance behavior was observed in the presence of imidacloprid (AC₅₀ = 0.11 mg kg^?1), captan (AC₅₀ = 33.54 mg kg^?1), carboxin + thiram (AC₅₀ = 60.32 mg kg^?1), and thiametoxam (AC₅₀ = >20 mg kg^?1). Earthworms showed a preference for soils with the insecticide fipronil. Imidacloprid was the most toxic of the substances tested for E. andrei. The avoidance test was the most sensitive test for most pesticides studied, but results varied between pesticides. These results offer new insights on the toxicity of pesticides used to treat seeds in tropical regions. However, they should be complemented with higher-tier tests in order to reduce the uncertainties in risk assessment.     

Influence of competing inorganic cations on the ion exchange equilibrium of the monovalent organic cation metoprolol on natural sediment

The aim of this study was to systematically investigate the influence of the mono- and divalent inorganic ions Na⁺ and Ca²⁺ on the sorption behavior of the monovalent organic cation metoprolol on a natural sandy sediment at pH = 7. Isotherms for the beta-blocker metoprolol were obtained by sediment–water batch tests over a wide concentration range (1–100 000 μg L^?1). Concentrations of the competing inorganic ions were varied within freshwater relevant ranges. Data fitted well with the Freundlich sorption model and resulted in very similar Freundlich exponents (n = 0.9), indicating slightly non-linear behavior. Results show that the influence of Ca²⁺ compared to Na⁺ is more pronounced. A logarithmic correlation between the Freundlich coefficient K_Fr and the concentration or activity of the competing inorganic ions was found allowing the prediction of metoprolol sorption on the investigated sediment at different electrolyte concentrations. Additionally, the organic carbon of the sediment was completely removed for investigating the influence of organic matter on the sorption of metoprolol. The comparison between the experiments with and without organic carbon removal revealed no significant contribution of the organic carbon fraction (0.1%) to the sorption of metoprolol on the in this study investigated sediment. Results of this study will contribute to the development of predictive models for the transport of organic cations in the subsurface.     

Development and characterization of cell line from the gill tissue of Catla catla (Hamilton, 1822) for toxicological studies

Catla gill cell line (ICG) was established from gill tissue of Indian major carp (Catla catla), a freshwater fish cultivated in India. The cell line was maintained in Leibovitz’s L-15 supplemented with 10% fetal bovine serum. These cells have been sub-cultured more than 55 passages over a period of 2 years. The ICG cell line consists predominantly of epithelial-like cells. The cells were able to grow at a wide range of temperatures from 24 °C to 32 °C with an optimum temperature of 28 °C. The growth rate of gill cells increased as the fetal bovine serum (FBS) proportion increased from 2% to 20% at 28 °C with optimum growth at the concentrations of 10% or 15% FBS. Amplification of mitochondrial gene 12s rRNA using primers specific to C. catla confirmed the origin of this cell line from C. catla. The cells were successfully cryopreserved and revived at passage numbers 25, 35, 45 and 55. The cytotoxicity of three metal salts (ZnCl₂, CuSO₄ and CdCl₂) was assessed in ICG cell line using multiple endpoints such as MTT, Neutral Red assay, Alamar Blue assay and Coomassie Blue protein assay. Acute toxicity assay on fish were conducted by exposing C. catla for 96 h to three metal salts under static conditions. Statistical analysis revealed good correlation with r² = 0.908–0.985 for all combinations between endpoints employed. Linear correlations between each in vitro EC₅₀ and the in vivo LC₅₀ data were highly significant.     

Deriving freshwater quality criteria for copper,cadmium, aluminum and manganese for protection of aquatic life in Malaysia

Freshwater quality criteria for copper (Cu), cadmium (Cd), aluminum (Al), and manganese (Mn) were developed with particular reference to aquatic biota in Malaysia, and based on USEPA’s guidelines. Acute toxicity tests were performed on eight different freshwater domestic species in Malaysia, which were Macrobrachium lanchesteri (prawn), two fish – Poecilia reticulata and Rasbora sumatrana, Melanoides tuberculata (snail), Stenocypris major (ostracod), Chironomus javanus (midge larvae), Nais elinguis (annelid), and Duttaphrynus melanostictus (tadpole), to determine 96-h LC50 values for Cu, Cd, Al, and Mn. The final acute values (FAVs) for Cu, Cd, Al, and Mn were 2.5, 3.0, 977.8, and 78.3 μg L^?1, respectively. Using an estimated acute-to-chronic ratio (ACR) of 8.3, the value for final chronic value (FCV) was derived. Based on FAV and FCV, a Criterion Maximum Concentration (CMC) and a criterion Continuous Concentration (CCC) for Cu, Cd, Al, and Mn of 1.3, 1.5, 488.9, and 39.1 μg L^?1 and 0.3, 0.36, 117.8, and 9.4 μg L^?1, respectively, were derived. The results of this study provide useful data for deriving national or local water quality criteria for Cu, Cd, Al, and Mn based on aquatic biota in Malaysia. Based on LC50 values, this study indicated that R. sumatrana, M. lanchesteri, C. javanus, and N. elinguis were the most sensitive to Cu, Cd, Al, and Mn, respectively.     

Swine wastewater treatment in a two stage sequencing batch reactor using real‐time control

Abstract

A laboratory scale two‐stage sequencing batch reactor (TSSBR) was used to study the effectiveness of pH as a real‐time control parameter in swine wastewater treatment. A Ringlace media was inserted into the A/O (Anoxic/Oxic) reactor for bacteria immobilization. The TSSBR was subjected to three levels of organic loading. The pH and ORP (Oxidation Reduction Potential) patterns obtained were consistent with distinct features, enabling the real‐time control strategy to effectively set a flexible aeration time pending on influent concentration, hence resulting in flexible cycle time and HRT (Hydraulic Retention Time) for the system. The real‐time process ensured a removal efficiency of over 99% and 95%, respectively, for ammonia and TOC (Total Organic Carbon). For NO₃ ^‐‐N and PO₄ ^‐3, the run with influent TOC = 4,000 mg/L yielded the most efficient removal of 61% and 95%, respectively. Test results suggest that pH can be a viable tool for on‐line real‐time control of a biological treatment process.     

Comparative acute toxicity of two phytosanitary molecules,lambda-cyhalothrin and acetamiprid,on Nile Tilapia (Oreochromis Niloticus) juveniles

Abstract

This study aimed to compare the toxicity for fish of two active ingredients (lambda-cyhalothrin-20?g L^?1, a pyrethroid, and acetamiprid-15?g L^?1, a neonicotinoid) which are components of a commercial insecticide (Acer 35 EC) used in cotton crop in many West African countries. The juveniles of Oreochromis niloticus (4.01?±?0.34?g, mean body weight) were exposed for 96?h to increasing concentrations of active ingredients (lambda-cyhalothrin and acetamiprid) or a mixture similar to Acer 35 EC (composed by 20?g of chemical compound lambda-cyhalothrin and 15?g of acetamiprid dissolved in 1?L of acetone). The experiments were carried out under controlled conditions in aquaria according to OECD Guidelines. During the experiments, the behavioral responses (loss of balance, color change, hyperactivity, etc.) that usually precede death were observed in exposed fish. Mortalities were recorded in each aquarium and the LC₅₀-96h of each chemical was determined. The LC₅₀-96h obtained were respectively 0.1268, 0.0029, 182.9 and 0.5685?ppm for Acer 35 EC, lambda-cyhalothrin, acetamiprid and mixture. All insecticides used in this study had profound impact on Nile tilapia behavior which may confirm the neurotoxicity of each single active compound as well as of their mixture.     

Measurement of Automobile Exhaust GAS Hydrocarbons

While snowflakes fell and Christmas carols heralded the imminent holiday, over 3000 delegates to the Third National Conference on Air Pollution were told to “Control Now for Clean Air.”

They were told this in many ways by many people—by the Vice President of the United States; by the Secretary of the Department of Health, Education, and Welfare who summoned the Conference; and by senators, congressmen, governors, and mayors.

Then eight panel sessions convened to discuss and to determine how to control now for clean air. Speakers from every section of American life addressed themselves to this subject; when they were finished, the eight session chairmen summarized what had been said, what had been, learned. These summaries appear on the following pages.     

A Simulation Model for Air Pollution over Connecticut

A different approach to mathematically modeling large-scale atmospheric processes is presented. Whereas past approaches have been to develop a model based on an accumulation of information from a specific geographical area, resulting in a model applicable to that area only, we have developed a general mathematical model applicable to any geographical area. The model’s applicability is controlled by specifying the input information describing the meteorological situation and pollution source configuration. A rectangular array of grid points is used to specify both the wind field, by using stream functions, and the average source strength of some pollutant for the area represented by the grid. The diffusion problem is divided into two areas: transport by the mean wind field, and dispersion based on travel time and distance as described by empirical equations. Trajectories of pollutants are traced backwards from the points of interest in the course of the calculations and the contributions of all sources that affect the points of interest are accumulated. The model requires an array of source strength information. An inventory of pollution sources in the State of Connecticut was compiled and maps of source strengths were prepared for five pollutants on a 5000-ft grid-square array. Maps of sulfur dioxide and carbon monoxide source strengths are presented with the resulting concentration distribution for “typical” meteorological conditions. The model permits the changing of meteorological or source values at predetermined intervals so that diurnal changes are incorporated in the calculations. The model has not been verified, but the values of pollution concentration are the right order of magnitude and the resulting patterns are as expected.     

enforcement of diesel smoke emissions for the state of new jersey

This paper reports on the research program undertaken by the State of New Jersey to determine those tests and instruments which can be used by authorized state agencies for the enforcement of diesel smoke emissions. The state agencies under consideration for the enforcement of diesel smoke emissions are the following: (1) The Division of Motor Vehicles, in its system of state owned inspection stations, will be able to inspect all diesel-powered trucks, and tractors which are registered in New Jersey. (2) The Public Utilities Commission will be able to inspect at their home garages all buses registered in the State. (3) The New Jersey State Police will be able to inspect diesel-powered vehicles on the road. It was decided that the maximum inspection time for each vehicle was not to exceed one minute. On the basis of the one minute per vehicle requirement, eight different tests were evaluated to determine which ones correlated well with normal vehicle operation. These tests included acceleration of a fixed external inertia, free acceleration of only the moving parts of the engine, three ramp tests, a test in which a heavy vehicle was towed, and a driving test in which the vehicle being tested was actually accelerated. The results of tests demonstrated that the modified free acceleration method correlates reasonably well with a loaded steady state cycle, distinguishes the high emitters and is simple to perform. Consequently, the free acceleration test method is recommended for use in inspection stations and on the road. Finally, nearly two hundred vehicles have been tested by this procedure to determine present and potential levels of diesel smoke emissions. Another phase of the program consisted of the determination of smoke measuring techniques and instrumentation. The use and design of smokemeters were extensively investigated, as well as the use of the visual and photographic techniques. Of the various smokemeters tested for this application, several measured smoke satisfactorily in the laboratory, but none were found adequate for field use; they either lacked portability or were unstable due to the deposition of soot on the optics. At the time of writing, specifications for the necessary smokemeter have been drafted and published for bid to interested manufacturers.