Matrine and oxymatrine in corroborant plant extracts and fertilizers: HPLC/MS-MS method development and single-laboratory validation

A reversed phase high-performance liquid chromatographic method (HPLC/MS-MS) has been developed and validated for detection of alkaloids matrine and oxymatrine in fertilizer with labeled enhancer plant defense activities. The analytical method was validated statistically. The results show a strong matrix effect, requiring quantification by standard addition method. The regression lines showed r² > 0.994. Recoveries ranging from 97 to 104% were obtained for the fortification level of 0.01% wt wt^?1 and the relative standard deviations ranged from 3 to 4% (n = 10). The limits of detection were below 0.0001% wt wt^?1, while the limits of quantification did not exceed 0.0004% wt wt^?1. The method is currently applied in ICQRF Laboratory of Catania on fertilized and corroborant plant extract collected in the Italian market in the frame of MIPAAF institutional quality control activity, with the aim to dectect these unpermitted active substances.     

Some toxicological aspects op methamidophos exposure in mice 1

Abstract

Cholinesterase activity in the brain, RBC and plasma of Swiss mice was determined following different routes of administration of methamidophos. Continuous feeding with the insecticide caused a progressive inhibition of both plasma‐ and erythrocyte enzymes. The effect of methamidophos was more pronounced when applied in diet than when administered dermally or intraperitoneally. Following a single injection (i.p.) of methamidophos, the brain enzyme showed maximum inhibition 24 hr following treatment. At the appearance of tremors, the plasma and RBC‐enzymes showed considerable inhibition, the former being more inhibited. The plasma enzyme appears to be the most sensitive enzyme and may be taken as a suitable index for exposure to methamidophos.     

Clinical effects and cholinesterase activity changes in workers exposed to phorate (Thimet)

Abstract

Phorate (Thimet), an aliphatic derivative of phospnorus is a hignly toxic insecticide. In order to implement the safety measures, the clinical manifestations and cholinesterase (ChE) activity were evaluated before and after 2 weeks of exposure to this insecticide in 40 male tormulators.

The 2 week's exposure reveal signs and symptoms of toxicity in 60% of the formulators. Gastrointestinal symptoms and lowering of heart rate (bradycardia) were more prominent as compared to the neurological symptoms. A significant depression in plasma ChE activity was observed at the end of 1st week (55%) and 2nd week (71%) as compared to the respective pre‐exposure values. A recovery up to 79% of the pre‐exposure activity of this enzyme was noticed 10 days after cessation of the above exposure.     

Contributions to ecological chemistry CXII balance of conversion of buturon‐14C in wheat under outdoor conditions 1

Abstract

The urea herbicide buturon (N‐[p‐chlorophenyl] ‐N’ ‐methyl‐N’ ‐isobutinyl‐urea), ¹⁴C‐labeled, was sprayed on winter wheat as an aqueous formulation (2.98 kg/ha) under outdoor conditions. Upon harvest (three months after application), a total of 49. 2% of the applied radiocarbon was recovered: 2.0% in the plants, 46.9% in the soil, and 0.3% in the leaching water (depth > 50 cm); less than 0.1% was in the grains (0.464 ppm). Only about half of the radioactivity present in plants could be recovered under mild extraction conditions; about half of this was unchanged buturon. In straw and husk extracts, the following metabolites were identified by gaschromatography/mass spectrometry: N‐(p‐chlorophenyl)‐N‐methyl‐O‐methyl‐carbamate (metabolite I), N‐phenyl‐N’ ‐formyl‐urea (metabolite II), two unstable metabolites giving (p‐chlorophenyl)‐isocyanate upon purification (metabolites III and IV), N‐(p‐chlorophenyl)‐N’ ‐methyl‐N’ ‐isobutenylol‐urea (metabolite V), p‐chloroformanilide (metabolite VI) and biologically bound p‐chloroaniline (metabolite VII). In the root and basal stem extract, the following metabolites were identified by gas chromatography/mass spectrometry: N‐(p‐chlorophenyl)‐O‐methyl‐carbamate (metabolite VIII) and N‐(p‐chlorophenyl)‐N’ ‐methyl‐urea (metabolite IX).     

Effect of some xenobiotics on kynurenine hydrolase and kynurenine aminotransferase of mouse liver

Abstract

The effects of some xenobiotics on the activity of the B₆‐dependent kynurenine hydrolase (KH) and kynurenine aminotransferase (KATE) in mouse liver, were investigated. Polychlorinated biphenyl (Aroclor 1254) (400mg/kg/day ×4) markedly decreased the activity of both enzymes. Benzo(a)pyrene (BP) and 3‐methylcholanthrene (3‐MC) (40mg/Kg/day ×1) as well as phénobarbital (PB) (75mg/kg/day ×3) did not alter the activity of KH, while that of KATE was mildy reduced. The response of the two enzymes to treatment with chlorpromazine (CPZ) (5mg/Kg/day ×5) were opposite with marked elevation of KH and inhibition of KATE activities. Treatment with B‐naphthoflavone (B‐NF) (80mg/Kg/day ×2), Pyrazole (200mg/Kg/day ×1) or indole (400mg/kg/day ×1) produce no change in the activity of either enzyme. It, seems therefore, that Aroclor(1254) and chlorpromazine may cause disordered kynurenine metabolism through alterations in the activities of its metabolizing enzymes. This, in turn, might affect nicotinamide adenine dinucleotide biosynthesis and/or the accumulation of some tryptophan metabolites suspected of being carcinogenic or co‐carcinogenic.     

A theoretical overview of the relationship between the resource curse and genuine savings as an indicator for “weak” sustainability

This paper shows the strong relation between the factors that lead to the resource curse (RC) and factors that lead to a decline of genuine savings (GS). There is substantial empirical evidence that economies that rely predominantly on their natural resources are also characterized by slower economic growth. This so‐called RC is commonly traced back to the fact that natural resources' generate rents that are independent of a country's economic performance, which can lead to suboptimal reinvestments of this consumed natural capital. We argue that the factors responsible for the RC also have a negative effect on GS, a concept that measures “weak” sustainable development by considering reinvestment of natural capital rents in physical and human capital. We discuss whether the RC hampers possibilities for resource abundant countries to obtain sufficiently high rates of GS, and find indeed many reasons why resource‐dependent countries have problems achieving positive GS rates. We survey both areas of research, emphasizing the influence of the exogenous and endogenous determinants of economic growth, which are usually used to theoretically and empirically explain the RC on the three different forms of capital considered by GS. We specify why most countries suffering from the RC have negative GS rates and explain in detail where the linkages are. This overview could help with potential advancements in the explanation of GS through the inclusion of RC effects.     

Reconstructions of Soil Moisture for the Upper Colorado River Basin Using Tree‐Ring Chronologies1

Anderson, SallyRose, Glenn Tootle, and Henri Grissino‐Mayer, 2012. Reconstructions of Soil Moisture for the Upper Colorado River Basin Using Tree‐Ring Chronologies. Journal of the American Water Resources Association (JAWRA) 48(4): 849‐858. DOI: 10.1111/j.1752‐1688.2012.00651.x Abstract: Soil moisture is an important factor in the global hydrologic cycle, but existing reconstructions of historic soil moisture are limited. We used tree‐ring chronologies to reconstruct annual soil moisture in the Upper Colorado River Basin (UCRB). Gridded soil moisture data were spatially regionalized using principal components analysis and k‐nearest neighbor techniques. We correlated moisture sensitive tree‐ring chronologies in and adjacent to the UCRB with regional soil moisture and tested the relationships for temporal stability. Chronologies that were positively correlated and stable for the calibration period were retained. We used stepwise linear regression to identify the best predictor combinations for each soil moisture region. The regressions explained 42‐78% of the variability in soil moisture data. We performed reconstructions for individual soil moisture grid cells to enhance understanding of the disparity in reconstructive skill across the regions. Reconstructions that used chronologies based on ponderosa pines (Pinus ponderosa) and pinyon pines (Pinus edulis) explained more variance in the datasets. Reconstructed soil moisture data was standardized and compared with standardized reconstructed streamflow and snow water equivalent data from the same region. Soil moisture and other hydrologic variables were highly correlated, indicating reconstructions of soil moisture in the UCRB using tree‐ring chronologies successfully represent hydrologic trends.     

Lindane removal by pure and mixed cultures of immobilized actinobacteria

Stereoselective dissipation of epoxiconazole had been studied in grape and soil during plant growing under field conditions in this paper. A sensitive and rapid chiral method was developed and validated for the determination of epoxiconazole stereoisomers in grape and soil based on liquid chromatography coupled with triple quadrupole mass spectrometry (LC-MS/MS). Phenomenex Lux Cellulose-1 column was used for enantioseparation with a mixture of acetonitrile/water (90/10, v/v) as mobile phase at flow rate of 0.3 mL min⁻¹. Fortified recoveries in grape and soil samples ranged from 76.0% to 91.9% and relative standard deviations were less than 11.4% with fortified levels of 0.025-1.0 mg kg⁻¹. The limits of detection and quantification were 0.005 mg kg⁻¹ and 0.025 mg kg⁻¹, respectively, with linear calibration curves extending up to 5.0 mg kg⁻¹. The field experimental results showed that dissipations of epoxiconazole stereoisomers in grape followed first-order kinetics (R² > 0.92) and stereoselectivity occurred in 2 h after spraying. The (−)-stereoisomer with half-life of 9.3 d degraded faster than (+)-stereoisomer with that of 13.2 d, and resulted in relative enrichment of (+)-stereoisomer. However, the stereoisomeric dissipations in soil were triphasic (“increase-decrease-steady”) with lower dissipation rates, and also occurred with preferential degradation of (−)-stereoisomer under field condition. The results for stereoselective dissipations can be applied for food and environmental assessments of chiral pesticides.     

Building the role of local government authorities towards the achievement of the human right to water in rural Tanzania

In recent decades, many changes have occurred in the approach to financing and operating water services in developing countries. The demand‐responsive approach is now adopted in many countries in a context of donor‐supported decentralization processes, which gives more responsibility to end users. However, the government's responsibility at different levels is enforced by the international recognition of the human right to water. This paper examines specific actions that build the role of local government authorities in this scenario. A collaboration between an international NGO and a rural district in Tanzania from 2006 to 2009 is used as an action research case study that is representative of local capacity‐building needs in decentralized contexts and rural areas. Three main challenges were detected: i) lack of reliable information; ii) poor allocation of resources in terms of equity; and iii) lack of long‐term community management support from the district. Two mechanisms were established: i) water point mapping as a tool for information and planning; and ii) a District Water and Sanitation Unit Support (DWUS) for community management. The results show how the framework provided by the goal of human right to water helps to define useful strategies for equity‐oriented planning and post‐project support at the local level.