Determination of organochlorine pesticide residue in sediment and water from the Densu river basin, Ghana

The distribution of organochlorine pesticides in the aquatic ecosystem from the Densu river revealed varying levels of concentration in water and the sediment samples. Three locations were sampled along the river to evaluate the levels of organochlorine pesticide residue in the river. Sediment and surface water samples were extracted by soxhlet and liquid-liquid extraction respectively and analyzed using Gas Chromatograph coupled with electron capture detector. The detectable organochlorine pesticides were gamma-hexachlorocyclohexane (HCH), delta-hexachlorocyclohexane, heptachlor, aldrin and dieldrin. The other pesticides that were investigated are gamma-chlordane, alpha endosulfan, endosulfan sulfate, p,p′-DDT and its metabolite p,p′-DDE, methoxychlor, endrin and its metabolite endrin aldehyde and endrin ketone. The order of increasing frequency of detection of samples was higher in sediment than water. In sediment, the mean concentration ranged from 0.030 μg kg⁻¹ dry weight (endrin) to 10.98 μg kg⁻¹ dry weight (aldrin). The highest detected concentration of organochlorine in water was endosulfan sulfate with mean concentration of 0.185 μg L⁻¹. Analysis of variance indicated significant differences for most organochlorine pesticide residue in the sediment sampled from the various locations. Some of the levels of organochlorine pesticides detected in water were relatively high compared to guideline values set by World Health Organization and Australia and thus could be harmful if the trend is not checked.     

Assessment of the impact of pesticide residues on microbiological and biochemical parameters of tea garden soils in India

The main aim of this study was to assess the impact of pesticidal residues on soil microbial and biochemical parameters of the tea garden soils. The microbial biomass carbon (MBC), basal (BSR) and substrate induced respirations (SIR), β -glucosidase activity and fluorescein diacetate hydrolyzing activity (FDHA) of six tea garden soils, along with two adjacent forest soils (control) in West Bengal, India were measured. The biomass and its activities and biochemical parameters were generally lower in the tea garden soils than the control soils. The MBC of the soils ranged from 295.5 to 767.5 μ g g^{? 1}. The BSR and SIR ranged from 1.65 to 3.08 μ g CO₂-C g^{? 1} soil h^{? 1} and 3.08 to 10.76 μ g CO₂-C g^{? 1}h^{? 1} respectively. The β -glucosidase and FDHA of the soils varied from 33.3 and 76.3 μ g para-nitrophenol g^{? 1} soil h^{? 1} and 60.5 to 173.5 μ g fluorescein g^{? 1}h^{? 1}respectively. The tea garden soils contained variable residues of organophosphorus and organochlorine pesticides, which negatively affected the MBC, BSR, SIR, FDHA and β -glucosidase activity. Ethion and chlorpyriphos pesticide residues in all the tea garden soils varied from 5.00 to 527.8 ppb and 17.6 to 478.1 ppb respectively. The α endosulfan, β endosulfan and endosulfan sulfate pesticide residues in the tea garden soils ranged from 7.40 to 81.40 ppb, 8.50 to 256.1 ppb and 55 to 95.9 ppb respectively. Canonical correlation analysis shows that 93% of the total variation was associated with the negative impact of chlorpyriphos, β and α endosulfan and endosulfan sulfate on MBC, BSR and FDHA. At the same time ethion had negative impact on SIR and β -glucosidase. Data demonstrated that the pesticide residues had a strong impact on the microbial and biochemical components of soil quality.     

Development,validation of QuEChERS-based method for simultaneous determination of multiclass pesticide residue in milk,and evaluation of the matrix effect

Extraction and quantification of pesticide residue from the milk matrix at or below the established maximum residue limit (MRL) is a challenging task for both analytical chemists and the regulatory institutions to take corrective actions for the human health and safety. The main aim of the study is to develop a simple rapid and less expensive QuEChERS extraction and cleanup method for simultaneous analysis of 41 multiclass pesticide residue in milk by gas chromatography-electron capture detector (GC-ECD), followed by confirmation of the residues with gas chromatography-mass spectrometer (GC-MS). Effect of sorbent type, temperature, spiking concentration, matrix effect (ME), measurement uncertainty (MU), inter- and intra-assay repeatability, reproducibility of recovery, and trueness of the results were investigated to validate the effectiveness of the method. Limit of determination (LOD) and limit of quantitation (LOQ) for all the analytes ranged within 0.001–0.02 and 0.002–0.05 µg mL^?1, respectively. The % recovery of all the pesticides ranged between 91.38 and 117.56% with relative standard deviation (RSD) below 2.79%. The MU for all the analytes was ≤29% of respective LOQs, and except for few pesticides, the ME was largely negative. The method fulfilled all the SANTE guidelines and thus can be extended for routine analysis of multiclass pesticide residue in milk.     

The effect of initial concentration, co-application and repeated applications on pesticide degradation in a biobed mixture

A 180 d laboratory experiment was conducted to investigate the degradation rates of chlorpyrifos (10 and 50 mg kg(-1)) and metalaxyl (100 mg kg(-1)) separately and co-applied in a biomix constituted by topsoil, vine-branches and urban-waste-garden compost. The effect of repeated application of metalaxyl was also investigated. Microbial biomass-C (MBC) content and metabolic quotient (qCO(2)) were measured to evaluate changes in microbial biomass size and activity induced by the presence of the two pesticides. Degradation rate decreased with increasing concentration of chlorpyrifos in all treatments. Metalaxyl half-life was significantly reduced in co-application with chlorpyrifos indicating a synergic interaction between the two pesticides in favour of enhanced degradation rate for metalaxyl but not for chlorpyrifos. Furthermore, repeated application resulted in a sharp reduction of metalaxyl half-life from 37 d after first application to 4 d after third application. MBC content was negatively influenced by the addition of pesticides but it started to recover immediately, in both separate and co-applied treatments, reaching the control value when pesticide residues were about 50% of the initial concentration. The qCO(2) reached a steady-state after about 20 d in separately applied and 40 d in co-applied treatments, indicating a tendency to arrive at a new metabolic equilibrium. In conclusion, the biomix tested has been shown to degrade pesticides relatively fast and to have a microbial community that is varied enough to allow selection of those microorganisms able to degrade metalaxyl and chlorpyrifos.     

Effect of additives in the Neem formulations on deposition,volatilization and persistence of Azadirachtin in spruce foliage

Abstract

Foliar deposits, volatilization and persistence of azadirachtin‐A (AZ‐A) were investigated after application of four spray mixes prepared from a wettable powder (WP) and three emulsifiable concentrate (EC) formulations of neem. They were applied at the dosage rate of 50 g AI in 4 L/ha onto potted spruce seedlings in a laboratory spray chamber. Droplet‐size spectra and deposits were assessed using Kromekote^® card/glass plate collection units. Foliar residues [dislodgeable residues (DR), penetrated residues (PR) and total residues (TR)] of AZ‐A and their volatilization were measured by HPLC at different intervals of time up to 60 h after treatment. Differences in the droplet‐size spectra and deposit levels were observed among the four spray mixes due to the influence of additives present in them. Dissipation half‐lives (DT₅₀) of the DR, PR and TR in the foliage were low (range, 19.5 to 38.9 h) and varied according to the residue type and the spray mix used. The DT₅₀ values of the DR were consistently lower (range, 19.5 to 31.9 h) than those of the PR (range, 30.5 to 38.9 h) due to preferential loss of the surface residues. The low DT₅₀ values observed for the DR and TR in the foliage sprayed with the WP spray mix were attributed to the particulate nature of the deposit. AZ‐A volatilized appreciably from the DR rather than from the PR. The variations found in the amounts of AZ‐A volatilized (42 to 58%) and unaccountable (38 to 46%) from the initial TR values in spruce foliage, after 60 h, were attributed to the physical form of the deposits on the target surface and the influences of additives present in the different spray mixes.     

The effect of a woodstove changeout on ambient levels of PM2.5 and chemical tracers for woodsmoke in Libby,Montana

Residential woodstoves are the single largest source of PM_2.5 in Libby, MT, resulting in the community being designated as a nonattainment area for PM_2.5. Beginning in 2005, a community-wide woodstove changeout program was implemented that replaced nearly 1200 old stoves with EPA-certified units. In an effort to track the reduction of woodsmoke particles throughout the program, ambient PM_2.5 samples were collected before, during, and after the changeout. These samples were analyzed for seven selected woodsmoke tracers, including vanillin, acetovanillone, guaiacol, 4-ethylguaiacol (methoxyphenols), levoglucosan (sugar anhydride), abietic acid, and dehydroabietic acid (resin acids). Results of the changeout showed that PM_2.5 levels decreased by 20% during the changeout period, while levels of the seven chosen tracer compounds gave variable responses. Levoglucosan levels decreased by 50% while both resin acids increased after the changeout, suggesting a change in the chemistry of the particles. No trend was observed in the levels of methoxyphenols as a group over the changeout period. The results suggest that the concentrations of woodsmoke related PM_2.5 in the Libby airshed have decreased; however, the chemistry of the emitted particles also changed when old woodstoves were replaced with new EPA-certified stoves.     

Photocatalytic inactivation of Escherichia coli by natural sphalerite suspension: effect of spectrum, wavelength and intensity of visible light

The photocatalytic disinfection of Escherichia coli K-12 is investigated by the natural sphalerite (NS) under different spectra, wavelengths and intensities of visible light (VL) emitted by light-emitting-diode lamp (LED). The spectrum effect of VL on disinfection efficiency is studied by using white LED, fluorescent tube (FT) and xenon lamp (XE), which indicates that the “discreted peak spectrum” of FT is more effective to inactivate bacteria than “continuous spectrum” of LED and XE. Besides, the photocatalytic disinfection of bacteria is compared under different single spectrum (blue, green, yellow and red color) LEDs. The results show that the most effective wavelength ranges of VL for photocatalytic disinfection with the NS are 440-490 and 570-620 nm. Furthermore, a positive relationship is obtained between the disinfection efficiency and the VL intensity. The experiment shows that NS can completely inactivate 10⁷ cfu mL⁻¹E. coli K-12 within 8 h irradiation by white LED with the intensity of 200 mW cm⁻² at pH 8. Moreover, the destruction process of the cell wall and the cell membrane are directly observed by TEM. Finally, no bacterial colony can be detected within a 96 h regrowth test of inactivated bacteria, which reveals that the VL-photocatalytic disinfection leads to an irreversible damage to the bacterial cells.     

The effect of multiple soil applications of disulfoton on enhanced microbial degradation in soil and subsequent uptake of insecticidal chemicals by potato plants

Abstract

Potatoes were grown during 1992 in 2 m² plots of loam which had received 1, 2 or 3 annual treatments of Di‐Syston 15G, equivalent to 3.36 kg AI/ha, in furrow at planting. The presence of enhanced degradative activity to the sulfoxide and sulfone metabolites of disulfoton in the soil treated in the previous two years was confirmed by laboratory tests prior to the 1992 treatments. Soil, seed potato and foliage from the three treatments were analyzed for disulfoton and its sulfoxide and sulfone metabolites for 12 wk following planting/treatment. Disulfoton was the major insecticidal component of the soil, a minor component of the seed piece and was not detected (<0.02 ppm) in potato foliage. Disulfoton concentrations in each of the three substrates sampled were similar for the three treatments. Disulfoton sulfoxide and sulfone were the major insecticidal components of the seed piece and foliage. Their maximum concentrations in 1st year soil, seed pieces and foliage were ca. 2x, 2x and 6x, respectively, those measured in the 2nd and 3rd year treatments. The results demonstrate that enhanced microbial degradation of relatively minor insecticidal compounds in the soil can profoundly affect insecticide levels in the plant when these compounds are the major insecticidal components accumulated. The broader implications for crop protection using soil‐applied systemic insecticides are discussed.     

The effect of aldicarb on nematode population and its persistence in carrots,soil and hydroponic solution

Abstract

Aldicarb, Temik^® 15 G, was incorporated in furrows at 3.37 and 6.73 kg ai (active ingredent)/ha and carrots (Caucus carota L.) were directly seeded on the same day. The numbers of nematode larvae were significantly suppressed in the treated plots; averages were 249, 74, and 51/ 50 cc soil samples for control (0), 3.37 and 6.73 kg ai/ha, respectively. Aldicarb treatment resulted in a 28% yield increase as compared to the untreated. Aldicarb residue in carrots was 28 ppb for the low treatment and 46 ppb for the high. Residual levels in soil of high treatment declined from 6l to 31 ppb during two weeks prior to harvest, meanwhile, those in the low decreased slightly from 13 to 12 ppb. Carrots placed in hydroponic solution containing aldicarb 14.5 ppm for 6 days, had an aldicarb residue of 10.26 ppb and the hydroponic solution, 2.7 ppb. Persistence of aldicarb residue was in carrot > in soil > in hydroponic solution.     

The effect of soil:water ratios on the induction of isoproturon, cypermethrin and diazinon mineralisation

The rate of pesticide biodegradation does not remain constant with time, and is dependent on the physico-chemical properties of the soil and of the pesticide as well as on the biology of the soil. Prolonged or repeated contact between soil microbes and pesticides has been shown to result in an increase in the rate and extent of biodegradation. This work assessed the impact of the soil:water ratio on measurement of catabolic induction for ¹⁴C-isoproturon, ¹⁴C-diazinon and ¹⁴C-cypermethrin. Slurrying (1:1 and 1:3 soil:water) with agitation resulted in significantly higher rates and extents of mineralisation than the non-slurried system (P ? 0.05; 1:0 soil:water), except for the mineralisation of ¹⁴C-diazinon where the greatest extent of mineralisation occurred in non-slurried soil. Slurrying without agitation resulted in the significant lower mineralisation in all cases (P ? 0.05). There was a significant interaction between the soil:water ratio and length of contact (P ? 0.05). Whilst the use of slurried systems can enhance the extent and rate of mineralisation, there is no improvement in reproducibility, and so for the measurement of catabolic induction, the use of field conditions will lead to a more environmentally relevant measurement.     

The effect of oils on PAH, PCDD, PCDF, and PCB emissions from a spark engine fueled with leaded gasoline

The effect of synthetic and mineral oils on the formation of polyaromatic hydrocarbons (PAHs), polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), and biphenyls (PCBs) in emissions from a spark ignition engine was studied on a Skoda Favorit engine fueled with leaded gasoline. The test cycle simulated urban traffic conditions on a chassis dynamometer, in accordance with the ECC 83.00 test. The data for selected PAHs as well as PCDDs, PCDFs, and PCBs congener profiles are presented. PCDD/Fs emissions for an unused oil and the oil after 10000-km operation varied from 300 to 2000 fmol/m3, PCBs emissions from 75 to 178 pmol/m3, and PAHs emissions from 150 to 420 microg/m3. The content of PCBs in oils varied from 2 to 920 mg/kg.     

The effect of deoxynivalenol on the secretion activity,proliferation and apoptosis of porcine ovarian granulosa cells in vitro

The aim of this in vitro study was to examine the secretion activity, markers of proliferation and apoptosis in porcine ovarian granulosa cells (GCs) after deoxynivalenol (DON) addition. Ovarian granulosa cells were incubated with DON for 24h: 10, 100 and 1000 ng/mL, while the control group received no DON. The secretion of insulin-like growth factor I (IGF–I) and progesterone was determined by radioimmunoassay (RIA) and expression of cyclin B1, PCNA and caspase-3 by immunocytochemistry. IGF–I release by GCs was inhibited by DON, while progesterone release and the expression of cyclin B1 was stimulated by DON (at 1000 ng/mL but not at 10 and 100 ng/mL). PCNA expression was stimulated by DON (at 100 and 1000 ng/mL but not at 10 ng/mL). Caspase-3 expression was not influenced by DON treatment (at all doses). In conclusion, our results indicate, (1) a direct effect of DON on secretion of growth factor IGF-I and steroid hormone progesterone, (2) expression of markers of proliferation (cyclin B1 and PCNA) but not on the (3) expression of marker of apoptosis (caspase-3) in porcine ovarian granulosa cells. This in vitro study suggests the dose-dependent association of DON on porcine ovarian functions.     

The effect of certain intrinsic and extrinsic variables on the acute toxicity of selected organophosphorus insecticides to the mummichog,Fundulus heteroclitus

Abstract

The acute toxicity of two organophosphorus (OP) insecticides, azinphosmethyl and acephate, was evaluated in the mummichog, Fundulus heteroclitus. In addition, the effects of certain intrinsic (sex) and extrinsic (salinity and multiple toxicant interraction) variables on the toxic response were also investigated. Azinphosmethyl was by far the most toxic of the two OP insecticides with a 96h LC50 ～ 100,000 x lower than that for acephate. Slight sex differences were observed in the sensitivity of mummichogs to each of the OP insecticides with male fish being marginally more sensitive. Significant effects of low salinity stress were observed only with acephate exposure and, in this case, low salinity appeared to be slightly protective. In general, all of the insecticide mixtures (azinphosmethyl/endosulfan, azinphosmethyl/fenvalerate and acephate/fenvalerate) tested exhibited simple additive toxicity.