Nitrogen-fertilizer addition to an agricultural soil enhances biogenic non-extractable residue formation from 2-13C,15N-glyphosate.

Glyphosate and nitrogen (N) or (P) phosphorus fertilizers are often applied in combination to agricultural fields. The additional P or N supply to microorganisms might drive glyphosate degradation towards sarcosine/glycine or aminomethylphosphonic acid (AMPA), and consequently determine the speciation of non-extractable residues (NERs): harmless biogenic NERs (bioNERs) or potentially hazardous xenobiotic NERs (xenoNERs). We therefore investigated the effect of P or N-fertilizers on microbial degradation of glyphosate and bioNER formation in an agricultural soil. Four different treatments were incubated at 20 °C for 75 days as follows; I: no fertilizer (2-13C,15N-glyphosate only, control), II: P-fertilizer (superphosphate + 2-13C,15N-glyphosate, effect of P-supply), III: N-fertilizer (ammonium nitrate + 2-13C,15N-glyphosate, effect of N-supply) and IV: 15N-fertilizer (15N-ammonium nitrate + 2-13C-glyphosate, differentiation between microbial assimilations of 15N: 15N-fertilizer versus 15N-glyphosate). We quantified 13C or 15N in mineralization, extractable residues, NERs and in amino acids (AAs). At the end, mineralization (36-41 % of the 13C), extractable 2-13C,15N-glyphosate/2-13C-glyphosate (0.42-0.49 %) & 15N-AMPA (1.2 %), and 13C/15N-NERs (40-43 % of the 13C, 40-50 % of the 15N) were comparable among treatments. Contrastingly, the 15N-NERs from 15N-fertlizer amounted to only 6.6 % of the 15N. Notably, N-fertilizer promoted an incorporation of 13C/15N from 2-13C,15N-glyphosate into AAs and thus the formation of 13C/15N-bioNERs. The 13C/15N-AAs were as follows: 16-21 % (N-fertilizer) > 11-13 % (control) > 7.2-7.3 % (P-fertilizer) of the initially added isotope. 2-13C,15N-glyphosate was degraded via the sarcosine/glycine and AMPA simultaneously in all treatments, regardless of the treatment type. The percentage share of bioNERs within the NERs in the N-fertilized soil was highest (13C: 80-82 %, 15N: 100 %) compared to 53 % (13C & 15N, control) and to only 30 % (13C & 15N, P-fertilizer). We thus concluded simultaneous N & glyphosate addition to soils could be beneficial for the environment due to the enhanced bioNER formation, while P & glyphosate application disadvantageous since it promoted xenoNER formation.

Assessment of heavy metals and associated oxidative stress in occupationally exposed workers from Bannu and Karak Districts in Pakistan.

Heavy metals (HMs) are extensively found in occupationally exposed miners and industrial workers, which may cause serious health-related problems to the large workforce. In order to evaluate the impact of these toxic pollutants, we have investigated the effect of cadmium (Cd), chromium (Cr), copper (Cu), and lead (Pb) concentration on exposed workers of mining, and woolen textile mill and compared the findings with unexposed individuals. From each category like exposed workers (mining, and woolen mill textile site) and unexposed individuals, 50 blood samples were taken. The occurrence of HMs in a sample was investigated through atomic absorption spectrometry while the oxidative stress marker malondialdehyde (MDA) and antioxidant enzyme statuses such as superoxide dismutase (SOD) and catalase (CAT) were analyzed in exposed and control samples. The results showed significant (p < 0.05) variation in Cd, Cr, Cu, and Pb levels in exposed and control samples. The concentration of Cd in the blood of WMWs, KMWs, and control group was 5.75, 3.89, and 0.42 µg/dL, respectively. On the other hand, the concentration of Pb in the blood of WMWs, MWs, and control was 32.34, 24.39, and 0.39 µg/dL while the concentrations of Cr and Cu in the blood of WMWs, MWs, and control group were 11.61 and 104.14 µg/dL, 4.21 and 113.21 µg/dL, 0.32 and 65.53 µg/dL, respectively. An increase in MDA was recorded in the exposed workers' group as compared to control subjects, whereas SOD and CAT activities decreased. Meanwhile, MDA was significantly and positively (p < 0.01) correlated with HMs, while negative significant correlations were found among HMs with SOD and CAT.

Fate of glyphosate and its degradation products AMPA, glycine and sarcosine in an agricultural soil: Implications for environmental risk assessment.

Glyphosate can be biodegraded via the aminomethylphosponic acid (AMPA) and the sarcosine/glycine pathway leading to the formation of three intermediate products AMPA, sarcosine or glycine. The fate of the three intermediate compounds of glyphosate biodegradation including nature of non-extractable residues (NERs; harmless biogenic [NERsbiogenic] versus hazardous xenobiotic [NERsxenobiotic]) in soils has not been investigated yet. This information is crucial for an assessment of environmental risks related to the speciation of glyphosate-derived NERs which may stem from glyphosate intermediates. Therefore, we incubated 13C- and 15N-labeled glyphosate (2-13C,15N-glyphosate) and its degradation product AMPA (13C,15N-AMPA), sarcosine (13C3,15N-sarcosine) or glycine (13C2,15N-glycine) in an agricultural soil separately for a period of 75 days. 13C2-glycine and 13C3-sarcosine mineralized rapidly compared to 2-13C-glyphosate and 13C-AMPA. The mineralization of 13C-AMPA was lowest among all four compounds due to its persistent nature. Only 0.5% of the initially added 2-13C,15N-glyphosate and still about 30% of the initially added 13C,15N-AMPA was extracted from soil after 75 days. The NERs formed from 13C,15N-AMPA were mostly NERsxenobiotic as compared to other three compounds for which significant amounts of NERsbiogenic were determined. We noticed 2-13C,15N-glyphosate was biodegraded via two biodegradation pathways simultaneously; however, the sarcosine/glycine pathway with the formation of harmless NERsbiogenic presumably dominated.

Evaluation of CAN Bus Security Challenges.

The automobile industry no longer relies on pure mechanical systems; instead, it benefits from many smart features based on advanced embedded electronics. Although the rise in electronics and connectivity has improved comfort, functionality, and safe driving, it has also created new attack surfaces to penetrate the in-vehicle communication network, which was initially designed as a close loop system. For such applications, the Controller Area Network (CAN) is the most-widely used communication protocol, which still suffers from various security issues because of the lack of encryption and authentication. As a result, any malicious/hijacked node can cause catastrophic accidents and financial loss. This paper analyses the CAN bus comprehensively to provide an outlook on security concerns. It also presents the security vulnerabilities of the CAN and a state-of-the-art attack surface with cases of implemented attack scenarios and goes through different solutions that assist in attack prevention, mainly based on an intrusion detection system (IDS).

Mulch of plant residues at the soil surface impact the leaching and persistence of pesticides: A modelling study from soil columns.

Crop residues left on the soil surface as mulch greatly influence the fate of pesticides in conservation agricultural practices because most of the applied pesticide is intercepted by mulch before passing to the soil. Modelling of pesticide losses from wash-off and leaching will greatly improve our understanding of the environmental consequences of pesticides in these systems. The PASTIS model, which simulates water transfer, mulch decomposition, and pesticide dynamics, was adapted in this new version to model the interactions between pesticides and mulch in order to simulate the impact of mulch on pesticide dynamic. Parameters of mulch dynamics and pesticide degradation and retention processes were estimated using independent incubation experiments. The PASTIS model was tested with experimental laboratory data that were obtained from two pesticides (Glyphosate and s-metolachlor) applied to soil columns where mulch composed of maize and dolichos was placed at the soil surface impacted by two rain intensities (a high and infrequent intensity and a light and frequent intensity). Simulations indicated good agreement between simulated and experimental values. After 1 day, 45-46% of the pesticides leached from the mulch and 54-55% remained in the mulch for both pesticides and both rain intensities. During the experiment, pesticide wash-off was greater for the high and infrequent rain (56-57%) compare to light and frequent rain (39-45%) for both pesticides. A smaller amount of S-metolachlor washed off with the light and frequent rain intensity (39%) than glyphosate (45%) because of its lower desorption rate from mulch residues. Glyphosate was more degraded (37-45%) than s-metolachlor (17-37%), which agrees with preliminary incubation experiments that were used for parameter estimation. A sensitivity analysis indicated that the saturation index of mulch at which pesticides started their diffusion in the rainwater and the time of the first rainfall were the two parameters that influenced the most output variables of our model. This study suggests that the PASTIS model developed for pesticide dissipation in mulch is a useful tool to evaluate the potential risk of pesticide leaching to the groundwater in conservation agriculture systems.

Effect of rainfall regimes and mulch decomposition on the dissipation and leaching of S-metolachlor and glyphosate: a soil column experiment.

BACKGROUND: Interception by plant residues is a major process affecting pesticide persistence and leaching in conservation agriculture. Dissipation and leaching of S-metolachlor and glyphosate was studied in repacked soil columns covered with a mulch of maize and lablab residues. The columns were submitted to two contrasting simulated rainfall regimes: one with light but frequent rain (LF) and one with less frequent but more intense rain (HI). In both treatments, columns received the same amount of rainwater by the end of the experiment. RESULTS: Decomposing crop residues on the soil surface retained more than 50% of the applied amount of pesticide. S-metolachlor dissipation in mulch residues was faster under the LF rainfall regime. This was attributed to more humid surface conditions, under which mulch decomposition was also faster. The formation of metabolites of both molecules was higher under the LF rainfall regime. However, leaching of S-metolachlor and its metabolites to deeper soil layers was greater under the HI rainfall regime, whereas they accumulated in the surface layer under the LF rainfall regime. Glyphosate remained in the surface soil layer because of its strong adsorption capacity, whereas aminomethylphosphonic acid leached down in small amounts without any difference between the two rainfall regimes. CONCLUSION: The impact of mulch residues on herbicide dissipation was strongly dependent on molecule type and rainfall regime. © 2014 Society of Chemical Industry.

Adsorption and desorption behavior of selected pesticides as influenced by decomposition of maize mulch.

Assessing pesticide fate in conservation agricultural systems requires a detailed understanding of their interaction with decomposing surface crop residues (mulch). Adsorption and desorption behavior of glyphosate, s-metolachlor and epoxiconazole was investigated on maize mulch residues decomposed under laboratory and field conditions. Our conceptual approach included characterization of chemical composition and hydrophobicity of mulch residues in order to generate parameters to predict sorption behavior. Adsorption of s-metolachlor and epoxiconazole greatly increased with mulch decomposition, whereas glyphosate adsorption was less affected but its desorption was increased. Mulch characteristics including aromaticity, hydrophobicity and polarity indices were strongly correlated to Koc of the non-ionic pesticides. A predictive model based on compositional data (CoDa) analysis revealed that the sorption capacity of decomposing mulch can be predicted from descriptors such as aromatic and alkyl C corresponding respectively to lignin and NDF biochemical fractions. The decomposition degree of mulch residues should be taken into account while predicting the fate of pesticides.

Retroperitoneal oncocytoma: case report and review of the imaging features.

Oncocytomas are uncommon tumours that occur in a number of specific anatomical locations within the head, neck, chest, abdomen and pelvis. When occurring in the retroperitoneum, oncocytomas almost always arise from either the kidney or adrenal gland. With this case we present the imaging findings of an exceptionally rare retroperitoneal oncocytoma whose site of origin is neither the kidney nor adrenal gland.

Assessment of tumor invasion of the vena caval wall in renal cell carcinoma cases by magnetic resonance imaging.

PURPOSE: We evaluated the role of magnetic resonance imaging (MRI) in patients with renal cancer and inferior vena caval involvement with reference to its ability to characterize the extent and nature of inferior vena caval tumor extension and wall invasion. MATERIALS AND METHODS: The study included 12 consecutive patients with renal cancer and inferior vena caval involvement. All patients underwent imaging on a 1.5 Tesla MRI unit. Coronal, axial T1 and axial T2-weighted images were performed in all cases, while in 6 3-dimensional gadolinium enhanced magnetic resonance angiography and venography were also performed. Images were assessed for the extent and nature of tumor extension, that is tumor versus thrombus, and invasion of the inferior vena caval wall. Imaging results were compared with operative findings. RESULTS: On MRI the extent and nature of the inferior vena caval tumor was correctly defined in all cases. The sensitivity, specificity and accuracy of inferior vena caval wall invasion were 100%, 89% and 92%, respectively. CONCLUSIONS: In patients with renal cancer and inferior vena caval involvement MRI defines the tumor level in the inferior vena cava. It is also a sensitive technique for detecting vessel wall invasion and provides important preoperative information for surgical planning.