A multi-residue method for the determination of 90 pesticides in matrices with a high water content by LC-MS/MS without clean-up

A method using QuEChERS extraction and LC-MS/MS in electrospray positive ionisation mode was developed and validated for the analysis of 90 pesticides in a high water content matrix (tomato) in a single chromatographic run. To assess the intra-laboratory reproducibility of the method, validation was conducted on four different days by two different analysts. The validation data was treated using a spreadsheet developed in-house, which sets the most appropriate model for linear fit by determining whether the residuals of the calibration curves are homocedastic or heterocedastic. A statistical test for the significance of regression was also carried out. Calibration was always matrix-matched and the curves were obtained over the range 0.0075-0.10 or 0.020-0.125 mg kg(-1). Identification of analytes was based on retention times and MRM ratios. Recoveries were assessed at four different levels for each analyte and were between 73 and 106%, with relative standard deviations under reproducibility conditions of <20%. The measurement uncertainties of the method for each pesticide analysed were below 50%. Previous validation of the same method, applied to papaya samples and satisfactory results obtained in various proficiency tests with different high water content matrices, demonstrated the applicability of the method to these classes of commodities, without clean-up. The validated method will be applied routinely in the pesticide residues monitoring programme that constitutes the National Residue and Contaminant Control Plan of Brazil.     

Packet Delay Statistics of the Multichannel Selective-Repeat Automatic-Repeat-Request

In this paper, we conduct stochastic modeling and analysis of the packet end-to-end delay in a multichannel selective-repeat automatic-repeat-request (MSR-ARQ) protocol. In this protocol, the transmitter continuously transmits packets over multiple parallel channels and retransmits erroneously received packets with either dynamic or static packet-to-channel scheduling policy. Under the assumption that packets are always supplied at the transmitter, denoted by the saturated traffic condition, we analyze the steady state probability distribution function of the delay of an arbitrary packet, which is measured by the duration between the instant at which the packet is transmitted for the first time and the time it departs from the resequencing queue at the receiver. Using the analysis result, we numerically compute the distribution function for chosen values of the number of channels and the error rates to demonstrate the computational effectiveness of the result. With numerical and simulation results, we then study the performance of MSR-ARQ in terms of the mean packet delay and compare the two scheduling policies. It is shown that the dynamic scheduling achieves a better packet delay performance than the static scheduling. With the dynamic scheduling and the presence of difference between the error rates of parallel channels, the mean packet delay decreases as the difference between channels?? error rates increases. Moreover, the number of parallel channels has an insignificant impact on the mean packet delay, which shows that the use of parallel channels is favorable for the wireless or mobile communications to increase the data transmission rate while keeping the mean packet delay at an acceptable level.     

Large shift in source of fine sediment in the upper Mississippi river

Although sediment is a natural constituent of rivers, excess loading to rivers and streams is a leading cause of impairment and biodiversity loss. Remedial actions require identification of the sources and mechanisms of sediment supply. This task is complicated by the scale and complexity of large watersheds as well as changes in climate and land use that alter the drivers of sediment supply. Previous studies in Lake Pepin, a natural lake on the Mississippi River, indicate that sediment supply to the lake has increased 10-fold over the past 150 years. Herein we combine geochemical fingerprinting and a suite of geomorphic change detection techniques with a sediment mass balance for a tributary watershed to demonstrate that, although the sediment loading remains very large, the dominant source of sediment has shifted from agricultural soil erosion to accelerated erosion of stream banks and bluffs, driven by increased river discharge. Such hydrologic amplification of natural erosion processes calls for a new approach to watershed sediment modeling that explicitly accounts for channel and floodplain dynamics that amplify or dampen landscape processes. Further, this finding illustrates a new challenge in remediating nonpoint sediment pollution and indicates that management efforts must expand from soil erosion to factors contributing to increased water runoff.     

A charcoal- and blood-free enrichment broth for isolation and PCR detection of Campylobacter jejuni and Campylobacter coli in chicken

The microaerophilic nature of Campylobacter and its requirement of ～5% O(2) for growth have complicated its recovery from foods. The addition to the enrichment media of oxygen quenchers such as charcoal or blood could interfere with PCR for its detection. In this study, a two-step simple aerobic method for Campylobacter detection is proposed. A modification of the Tran blood-free enrichment broth (BFEB), in which charcoal was excluded from the medium (M-BFEB), was compared with the original formulation and other enrichment broths. Campylobacter jejuni and Campylobacter coli were screened by PCR directly from the enrichment media. Various levels of pure cultures of C. jejuni and C. coli combined with Escherichia coli were inoculated into Preston, Bolton, BFEB, and the modified BFEB (M-BFEB). In addition, Campylobacter was inoculated onto retail purchased chicken skin and recovery was quantified. Rates of recovery after 24 to 48 h of enrichment at 42 °C under aerobic incubation for BFEB and M-BFEB and microaerobic incubations for Preston and Bolton broths were determined. Overall, our results indicated that the most sensitive medium was Bolton's, followed by either BFEB or M-BFEB; the least sensitive was Preston's. M-BFEB was directly coupled to a PCR assay to detect Campylobacter, avoiding intermediate plating. Campylobacter was detected in the presence of up to 10(8) E. coli cells per ml. M-BFEB facilitated detection of both C. jejuni and C. coli artificially inoculated onto chicken skin samples. M-BFEB coupled to PCR is a rapid and attractive alternative for isolation and identification of C. coli and C. jejuni from poultry.     

Effects of Soil Water Salinity on Field Soil Hydraulic Functions

Unsaturated soil hydraulic parameters and functions used in numerical models to simulate water flow and solute transport in the unsaturated zone are generally considered invariant of soil water salinity levels. This study uses 5 years of field soil water salinity levels at three observation sites from the Land Retirement Demonstration Project (LRDP) (20069) located in western Fresno County, California, to test the hypothesis that field unsaturated soil hydraulic properties are also a function of soil water salinity level. The HYDRUS-1D software package for simulating one-dimensional (1D) movement of water, heat, and multiple solutes in variably saturated media, and Parameter Estimation (PEST), a model-independent parameter optimizer, is used to optimize the soil hydraulic parameters and downward bottom flux corresponding to three different average soil salinity levels at each site. The results show that at the same pressure head, soil water content is less with higher soil water salinity as compared with lower soil water salinity. It is thus concluded that the use of soil water salinity invariant soil water hydraulic parameters in numerical modeling can seriously compromise predictions, especially for a variable soil water salinity environment.     

Influence of dietary vitamin E on behavior of Listeria monocytogenes and color stability in ground turkey meat following electron beam irradiation

There is growing concern that the free radical scavenging effect of antioxidants added to meats might reduce the antimicrobial effectiveness of ionizing radiation. A study was conducted to determine the effect of vitamin E on the behavior (growth) of Listeria monocytogenes and color stability in turkey meat following electron beam irradiation. Raw ground turkey breast meat from birds fed diets containing 0 (control), 50, 100, and 200 IU/kg of vitamin E was inoculated with a five-strain mixture of L. monocytogenes to give approximately 10(7) CFU/g. Inoculated samples were irradiated at 0, 0.5, 1, and 2 kGy and stored aerobically (12 days) or under vacuum (42 days) at 4 degrees C. L. monocytogenes survivors were determined by plating samples on modified Oxford medium and counting colonies on modified Oxford medium plates after 48 h at 35 degrees C. Meat color was measured using a colorimeter. Irradiation at 2.0 kGy resulted in an approximately 3.5-log reduction of initial numbers of L. monocytogenes. There were no significant differences in D-values (decimal reduction times) for L. monocytogenes in meat irrespective of vitamin E treatment (P > 0.05). Also, vitamin E treatments did not affect growth of the pathogen in aerobic or vacuum-packaged samples following irradiation (P > 0.05). Compared with controls, irradiated meat from birds fed 100 or 200 IU/kg of vitamin E demonstrated significant improvement in color stability (lightness and redness values) during aerobic storage (P < 0.05). Dietary vitamin E (100 to 200 IU/kg) has good potential for improving the color stability of turkey meat without compromising the microbial safety of the irradiated product.     

Neurological Immunotoxicity from Cancer Treatment

The emergence of immune-based treatments for cancer has led to a growing field dedicated to understanding and managing iatrogenic immunotoxicities that arise from these agents. Immune-related adverse events (irAEs) can develop as isolated events or as toxicities affecting multiple body systems. In particular, this review details the neurological irAEs from immune checkpoint inhibitors (ICI) and chimeric antigen receptor (CAR) T cell immunotherapies. The recognition and treatment of neurological irAEs has variable success, depending on the severity and nature of the neurological involvement. Understanding the involved mechanisms, predicting those at higher risk for irAEs, and establishing safety parameters for resuming cancer immunotherapies after irAEs are all important fields of ongoing research.     

Multivariate Optimization for the Development of a Fast and Simple Ultrasound-Assisted Extraction Procedure for Multielemental Determination in Tea Leaves by Inductively Coupled Plasma Optical Emission Spectrometry (ICP OES)

The current study describes a fast and efficient procedure of ultrasound-assisted extraction for determination of Ca, Mg, K, Na, Cu, Zn, Mn, and Al in tea leaves by inductively coupled plasma optical emission spectrometry (ICP OES). The variables of procedure were optimized using the Box–Behnken design and the conditions selected were nitric acid concentration (1.0 mol L^?1), sonication time (7 min), and sonication temperature (75 °C). The extraction efficiency was calculated using the analyte concentration obtained by a total digestion procedure as reference. Accuracy was confirmed by analysis of certified reference material of apple leaves (NIST 1515) and spinach leaves (NIST 1570a) using the procedure proposed. A statistical evaluation using Student’s t test showed that there is no significant difference between the value obtained with the proposed procedure and the certified value, at 95% confidence level. The proposed procedure was successfully applied and is a good alternative to conventional acid digestion procedure and can be applied to routine analysis for determination of Ca, Mg, K, Na, Zn, Mn, Cu, and Al in tea leaves used for the preparation of infusions.     

Application of a multiplex polymerase chain reaction assay for the simultaneous confirmation of Listeria monocytogenes and other Listeria species in turkey sample surveillance

A multiplex polymerase chain reaction was developed to simultaneously identify Listeria monocytogenes and species of the genus Listeria. Two sets of primers were used, with the first amplifying a 938-bp region of the 16S rRNA gene that is highly conserved in all Listeria species and the second amplifying a 174-bp region of the listeriolysin (hlyA) gene of L. monocytogenes. Thus, isolates of Listeria spp. yield a single 938-bp product, whereas L. monocytogenes isolates yield both the 938-bp product and a 174-bp product. The specificity of the assay was verified with all six Listeria species and 11 serotypes of L. monocytogenes, as well as nonrelated bacteria. The multiplex PCR assay was used to determine the incidence of Listeria spp., especially L. monocytogenes, in mechanically separated turkey samples (n = 150 samples). L. monocytogenes strains were selected by using the University of Vermont two-step enrichment protocol and plating to selective Palcam agar. The multiplex PCR assay was used for verification of presumptive Listeria colonies. Approximately 38% of mechanically separated turkey samples (57 of 150) yielded L. monocytogenes; an additional 18% of these samples (27 of 150) harbored other Listeria spp. Fifty-one percent (29 of 57) of the L. monocytogenes isolates were of serogroup 1, 44% (25 of 57) were of serogroup 4, and 2% (1 of 57) were assigned to serogroups other than 1 and 4.     

Radiation chemistry of methyl tert-butyl ether in aqueous solution

The chemical kinetics of the free-radical-induced degradation of the gasoline oxygenate methyl tert-butyl ether (MTBE) in water have been investigated. Rate constants for the reaction of MTBE with the hydroxyl radical, hydrated electron, and hydrogen atom were determined in aqueous solution at room temperature, using electron pulse radiolysis and absorption spectroscopy (*OH and e- aq) and EPR free induction decay attenuation (*H) measurements. The rate constant for hydroxyl radical reaction of (1.71 +/- 0.02) x 10(9) M(-1) s(-1) showed that the oxidative process was the dominant pathway, relative to MTBE reaction with hydrogen atoms, (3.49 +/- 0.06) x 10(6) M(-1) s(-1), or hydrated electrons, <8.0 x 10(6) M(-1) s(-1). The hydroxyl radical reaction gives a transient carbon-centered radical which subsequently reacts with dissolved oxygen to form peroxyl radicals, the rate constant for this reaction was (2.17 +/- 0.06) x 10(9) M(-1) s(-1). The second-order decay of the MTBE peroxyl radical was 2k = (6.0 +/- 0.3) x 10(8) M(-1) s(-1). These rate constants, along with preliminary MTBE degradation product distribution measurements, were incorporated into a kinetic model that compared the predicted MTBE removal from water against experimental measurements performed under large-scale electron beam treatment conditions.