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).     

The electron density distribution in pyridinium and bipyridylium compounds and its relevance to their adsorption by expanding lattice clays

Abstract

Charge distributions in 1, 1'‐ethylene‐2, 2'‐bipyridylium (diquat), 1,1'‐dimethyl‐4,4'‐bipyridylium (paraquat) and 1‐methylpyridinium organocations were calculated by a Complete Neglect of Differential Overlap semi‐empirical quantum mechanical procedure. The data show that the positive charges in the organocations are distributed around the molecules and are greatest in the positions ortho and para to the heterocyclic nitrogen atoms. Earlier interpretations of the mechanisms of adsorption of paraquat and diquat by soils and clays assumed that the charges were located in the heterocyclic nitrogen atoms. Here some consideration is given to the influence of the charge delocalizations on the processes of adsorption by montmorillonite and vermiculite clay preparations.     

Volatilization of 1,2‐dibromo‐3‐chloropropane (DBCP) from soils

Abstract

The volatilization of DBCP from soils, as affected by the soil characteristics and application techniques, was studied in a laboratory experiment. The volatilization rate of DBCP applied in water was higher from sandy and silty loam soils than from clay soil. Water added after DBCP application acted as a soil cover, decreasing the volatilization rate. The results obtained with DBCP application in hexane to air‐dry soils, indicate that adsorption could be an important factor in reducing the volatilization losses.

Diffusion coefficients were calculated from the volatilization parameters, by using a simplified relationship between volatilization losses and diffusion through soil.     

Persistence and biodegradation of carbaryl in soils

Abstract

The persistence of the methylcarbamate pesticide carbaryl was studied in four soils under flooded conditions. A substantial portion of the pesticide was recovered from all soils even after 15 days of its application, with the recovery ranging from 37% in an alluvial soil to 73% in an acid sulfate soil. The degradation of carbaryl was more rapid under flooded conditions than under nonflooded conditions. A bacterium, Pseudomonas cepacia, isolated from a flooded soil amended with a related methylcarbamate pesticide carbofuran, degraded carbaryl in a mineral medium supplemented with yeast extract.     

Co-composting of Paper Mill Sludge and Hardwood Sawdust Under Two Types of In-Vessel Processes

Abstract

Recycling of organic residues by composting is becoming an acceptable practice in our society. Co-composting dewatered paper mill sludge (PMS) and hardwood sawdust, two readily available materials in Canada, was investigated using uncontrolled and controlled in-vessel processes. The composted materials were characterized for total C and N, water-soluble, acid-hydrolyzable, and non-hydrolyzable N, extractable lipids, and by Fourier Transform Infrared (FT-IR) spectrophotometry. In the controlled scale process, the loss of organic matter was approximately 65% higher than in the uncontrolled process. After undergoing initial fluctuations in N fractions during the first two days of composting, by the end of the process, concentrations of water-soluble N decreased while those of acid-hydrolyzable and nonhydrolyzable N increased in the controlled process, whereas in the uncontrolled process, water-soluble N increased, but N in the other two fractions decreased continuously, indicating that the biochemical transformations of organic matter were not completed. Data on extractable lipids and FT-IR spectra suggest that the compost produced from the controlled process was bio-stable after 14 days, while the uncontrolled process was not stabilized after 18 days. In addition, FT-IR data suggest the biological activity during composting centered mainly on the degradation of aliphatic structures while aromatic structures were preserved. The co-composting of the PMS and hardwood sawdust can be successfully achieved if aeration, moisture, and bio-available C/N ratios are optimized to reduce losses of N.     

Analysis of Herbicide Krovar I™ by Liquid Chromatography with Atmospheric Pressure Chemical Ionization Mass Spectrometry

Abstract

A simple, very efficient method is presented for routine analysis of herbicide Krovar I? (active components bromacil and diuron) in water and soil samples. Water samples were extracted by liquid–liquid extraction with dichloromethane (DCM) as extraction solvent. For soil samples two different extraction techniques were compared: microwave-assisted solvent extraction and a shaking technique using a platform shaker. Extracts were analyzed by high performance liquid chromatography using a water:methanol gradient. Liquid chromatography was coupled with atmospheric pressure chemical ionization mass spectrometry (LC-APCI-MS) for quantification of bromacil and diuron. Optimization of the APCI-MS was done by using standards in the flow injection analysis mode (FIA). Method detection limit for liquid samples for bromacil is 0.04 µg L^?1 and for diuron 0.03 µg L^?1. Method detection limit for soil samples is 0.01 µg g^?1 dry weight for both compounds. Results of analysis of field samples of water and soil are also presented.     

正交试验-硝酸微波消解-冷原子吸收法测定土壤中汞

应用硝酸微波消解土壤样品-冷原子吸收法测定土壤中的汞。通过正交试验,优化了土壤中汞的微波消解条件。并对干扰消除、方法精密度、加标回收、检出限进行了试验研究。在0～10μg／L范围内线性关系良好,方法测定下限为0．20μg／L,土壤中汞的检出限为0．005μg／g。该优化条件对汞含量为0．02—0．46μg／g的土壤样品,汞提取完全。建立了一种简便、成本低、干扰少、灵敏度高的方法。     

Some observations on copper yields and ore grades

The paper examines trends in the average copper content of mined ores over the years. It has tended to decline over the long term, but by no means evenly. US averages are not typical of global averages, at least in the past four decades. Those have been both higher, and less volatile than in the US. One reason for falling averages is a change in the type of deposit mined, with a rise in the share of relatively low grade porphyry deposits. The different nature of their deposits is reflected in marked differences in grades between the different continents. African and Australian average grades are higher than the global average, and changes in the share of Central Africa in global output have affected the global average grade. Yields are have been consistently lower in North America than elsewhere, and Latin American average grades have trended downwards, reflecting both the ageing of mines and the rising share of production from porphyry deposits. Typically the yield of mines declines over time as mining proceeds. The average copper content of ore deposits is usually below the average yield of the ore accessed in the early years of production. The initial grades of new mines have not declined over the past forty years, and there has been no perceptible tendency for the average grade of porphyry deposits brought into production to decline over time. There is no apparent correlation between average grade and deposit size, but mine operators tend to exploit economies of scale to offset low grades. The relationship between the annual percentage yields (the head grade) and the reserve grades of deposits is not static. In recent years head grades have fallen closer to reserve grades. The relationship may be affected by movements in metal prices. Although the evidence about the influence of prices is not clear-cut, it does suggest that prices and cut-off grades may be inversely related. As many ores contain other valuable metals besides copper, copper yields will sometimes be subordinated to the extraction of these other metals. Copper equivalent grades have not moved in the same way as copper grades alone.     

Enclave development and ‘offshore corporate social responsibility’: Implications for oil-rich sub-Saharan Africa

This paper critically reflects on the challenges of engaging, proactively, in Corporate Social Responsibility (CSR) in oil-rich sub-Saharan Africa. Most of the region's oil production takes place in enclave-type environments offshore and in countries ruled by autocratic governments which generally exert minimal pressure on companies to embrace CSR. With companies having little sense of who to target in their local economic development policies and programs, there is always a possibility of ‘offshore CSR’ – recognized here as potentially-effective ideas for improving social welfare that linger within the enclave and never fully materialize – surfacing. The aim is to conceptualize and broaden understanding of the challenge of developing CSR programs in these settings, where there are no clear linkages to communities or local economies more generally.     

微波消解-流动注射分光光度法测定土壤中的总磷

采用热效率高的微波消解系统对土壤中的总磷进行消解,建立了微波消解-流动注射分光光度法测定土壤中总磷的方法,该方法对比HJ632-2011碱熔-钼锑抗分光光度法具有快速、简便、节约试剂等特点。本文用两种分析方法对实际土壤样品及标准样品进行定量测定,所得结果表明微波消解法能快速测定大量土壤样品的总磷。