Distribution and persistence of carbaryl in some terrestrial and aquatic components of a forest environment

Abstract

An oil‐based formulation of carbaryl (1‐naphthyl N‐methyl‐carbamate) (Sevin‐2‐Oil) was applied twice by a fixed‐wing aircraft at a dosage rate of 280 g of A.I./ha/application to a coniferous forest near Allardville, New Brunswick. The highest concentrations of the chemical in fir foliage, litter and forest soil 1 h after application were respectively 4.20, 1.21 and 0.59 ppm (fresh weight). The residues dissipated rapidly and the DT50 values obtained from the depletion curves were 2.3 d for foliage and 1.5 d for litter and soil samples. Very low levels (<0.1 ppm) of carbaryl persisted in foliage and litter beyond the 10 d sampling period. The maximum residue level found in stream water was 0.314 ppm and more than 50% of it had dissipated within 1 h. Low but detectable levels (0.001 ppm) of the chemical persisted in water until the end of the 10 d sampling period. Sediment samples contained a maximum level of 0.04 ppm, which dissipated below the detection limit within 5 h. Brook trout and slimy sculpins captured in the stream 1 d after the spray contained on average about 0.04 ppm of carbaryl and none of it was found in 3 d postspray samples.     

Fate and availability of glyphosate and AMPA in agricultural soil

The fate of glyphosate and its degradation product aminomethylphosphonic acid (AMPA) was studied in soil. Labeled glyphosate was used to be able to distinguish the measured quantities of glyphosate and AMPA from the background values since the soil was sampled in a field where glyphosate had been used formerly. After addition of labeled glyphosate, the disappearance of glyphosate and the formation and disappearance of AMPA were monitored. The resulting curves were fitted according to a new EU guideline. The best fit of the glyphosate degradation data was obtained using a first-order multi compartment (FOMC) model. DT₅₀ values of 9 days (glyphosate) and 32 days (AMPA) indicated relatively rapid degradation. After an aging period of 6 months, the leaching risk of each residue was determined by treating the soil with pure water or a phosphate solution (pH 6), to simulate rain over a non-fertilized or fertilized field, respectively. Significantly larger (p < 0.05) amounts of aged glyphosate and AMPA were extracted from the soil when phosphate solution was used as an extraction agent, compared with pure water. This indicates that the risk of leaching of aged glyphosate and AMPA residues from soil is greater in fertilized soil. The blank soil, to which 252 g glyphosate/ha was applied 21 months before this study, contained 0.81 ng glyphosate/g dry soil and 10.46 ng AMPA/g dry soil at the start of the study. Blank soil samples were used as controls without glyphosate addition. After incubation of the blank soil samples for 6 months, a significantly larger amount of AMPA was extracted from the soil treated with phosphate solution than from that treated with pure water. To determine the degree of uptake of aged glyphosate residues by crops growing in the soil, ¹⁴C-labeled glyphosate was applied to soil 6.5 months prior to sowing rape and barley seeds. After 41 days, 0.006 ± 0.002% and 0.005 ± 0.001% of the applied radioactivity was measured in rape and barley, respectively.     

Dieldrin uptake by vegetable crops grown in contaminated soils

The aim of these trials was to study the distribution of dieldrin in soil and its translocation to roots and the aerial parts of vegetable crops grown in greenhouses and fields. The main objectives were to characterize dieldrin accumulation in plant tissues in relation to the levels of soil contamination; uptake capability among plants belonging to different species, varieties and cultivars. The presence of the contaminant was quantified by gas chromatography-electron capture detector (GC-ECD) and confirmed by gas chromatography-mass spectrometer (GC-MS). The results showed a translocation of residues in cucurbitaceous fruits and flowers confirming that zucchini, cucumber and melon are crops with high uptake capability. The maximum level of dieldrin residue at 0.01 mg/kg was found to be a threshold value to safeguard the quality production of cucurbits. Tomato, lettuce and celery were identified as substitute crops to grow in contaminated fields.     

基于响应曲面法优化烧结烟气脱硫灰改性工艺

采用BOX-Behnken的中心组合实验设计及响应面分析方法对半干法烧结烟气脱硫灰进行改性研究,得到脱硫灰转化率的预测模型。结果表明:通过该预测模型可以很好地描述脱硫灰的转化率与反应温度、反应时间和气固比等重要操作参数之间的关系,R2=0.9903。因素分析表明,反应温度对脱硫灰的转化率影响最大,同时反应温度和气固比的交互作用与反应温度和时间的交互作用对脱硫灰的转化率的影响作用相同。利用得到的改进预测模型可以计算脱硫灰的转化率。     

生物膜填料塔净化模拟烟气和电厂烟气中SO2和NOx的对比实验

对生物膜填料塔对模拟烟气和电厂烟气的净化效果进行了实验研究。实验对比分析了在相同的实验条件下生物膜填料塔对不同烟气中SO2和NOx的净化效率。实验结果表明，在循环液温度在24～35℃、空床停留时间（EBRT）为60s、喷淋量为8～10L／h、脱硫塔的pH为0．8～1．5、脱氮塔的pH为7．5～8．0的条件下，生物膜填料塔对模拟烟气和电厂烟气中SO2的净化效率都很高，但模拟烟气条件下的总脱氮率的平均值为80％，而在电厂烟气条件下只有35％。经分析认为，脱氮率产生差异的主要原因是电厂烟气中杂质的影响，以及烟气中氧气含量的不同，同时因为生长条件不同从而驯化出的微生物群体组成也不同。     

Limitations in the determination of maximum residue limits and highest residues of pesticides: Part I

The pesticide usages are controlled by comparing residue concentrations in treated commodities to legally permitted maximum levels (MRLs) determined based on supervised trials designed to reflect likely maximum residues occurring in practice following authorised use. The number of trials available may significantly affect the accuracy of estimated maximum residues. We conducted a study with synthetic lognormal distributions with mean of 1 and standard deviations of 0.8 and 1.0, which reflect the residue distributions observed in practice. The likely residues in samples were modelled by drawing random samples of size 3, 5, 10 and 25 from the synthetic populations. The results indicate that the estimations of highest residues (HR), used for calculation of short-term intake, and the MRLs, serving as legal limits, are very uncertain based on 3–5 trials indicated by the calculated HR_0.975/HR_0.025 and MRL_0.975/MRL_0.025 ratios of 12 and 9, and 13 and 10, respectively, which question the suitability of such trials for the intended purpose. As the 95% range of HR and MRL rapidly decreases with number of trials, ideally ≥15 but minimum 6–8 trials should be used for estimation of HR and MRL according to the current typical practice of Codex Alimentarius.     

NiO-CuO/ZSM-5催化剂对催化裂化烟气的脱硫脱硝性能

采用浸渍法制备了不同NiO和CuO质量分数的NiO-CuO/ZSM-5催化剂，并以CH4为还原剂研究了NiO-CuO/ZSM-5催化剂对催化裂化烟气的脱硫脱硝活性。XRD分析结果表明，NiO质量分数为4%、CuO质量分数为6%的催化剂4%NiO-6%CuO/ZSM-5中的ZSM-5结构完好，CuO和NiO高度分散在ZSM-5骨架中，表明具有较好的催化活性。4%NiO-6%CuO/ZSM-5的脱硫脱硝起活温度均较低，无氧条件下最高NO转化率和SO2转化率分别为94.7%和95.9%，O2体积分数为1.0%时的NO转化率和SO2转化率分别为97.7%和89.0%。     

碱式硫酸铝溶液中SO42-的测定

建立了以铬黑T为指示剂，乙二胺四乙酸二钠反滴定过量BaCl₂的碱式硫酸铝溶液中SO₄^2-的测定方法。实验确定的操作条件为：待测试样稀释后ρ（SO_4^2-）为0.025 ~0.100 g/L，BaCl₂过量率为25%~100%，并且在加入BaCl₂前将试样煮沸，三乙醇胺加入量为0.10 L/L。该法回收率在98.90%~100.72%，相对标准偏差小于1%。测定方法准确，可靠，且操作简便、快速。     

烟气同时脱硫脱硝化学反应的可能性分析

根据烟气气体组分情况，将可能发生的化学反应方程式进行筛选，确定独立反应个数。通过热力学计算得到了标准状态下热力学函数值，进而求得了不同温度下的热力学性质。通过标准生成自由焓、标准吉布斯自由能变、标准熵变的计算，分析了烟气同时脱硫、脱硝中发生化学反应的可能性，为烟气同时脱硫、脱硝动力学理论的研究打下了基础。     

A correlation between the fate and non-extractable residue formation of 14C-metalaxyl and enzymatic activities in soil

Extracellular, oxidative soil enzymes like monophenol oxidases and peroxidases play an important role in transformation of xenobiotics and the formation of organic matter in soil. Additionally, these enzymes may be involved in the formation of non-extractable residues (NERs) of xenobiotics during humification processes. To examine this correlation, the fate of the fungicide ¹⁴C metalaxyl in soil samples from Ultuna (Sweden) was studied. Using different soil sterilization techniques, it was possible to differentiate between free, immobilized, and abiotic (“pseudoenzyme”-like) oxidative activities. A correlation between the formation of metalaxyl NER and soil organic matter content, biotic activities, as well as extracellular phenoloxidase and peroxidase activities in the bulk soil and its particle size fractions was determined. Extracellular soil-bound enzymes were involved in NER formation (up to 8% of applied radioactivity after 92 days) of the fungicide independently from the presence of living microbes and different distributions of the NER in the soil humic subfractions.