The degradation of methyl bromide in some natural fresh waters. influence of temperature,pH and light

The influence of some chemical and physical factors (pH, temperature and light) on degradation (hydrolysis) and volatilisation of methyl bromide (MB) from natural fresh waters was investigated. The complexity of the processes involved in MB persistence was shown. Under static and air-free conditions the half-life is quite long (30-50 days) but is decreased by an increase in pH and temperature (9-10 days), by UV irradiation (10-12 days) and, most of all, by exposure to air and shaking of the solution (2 h) and by soil.     

苦参碱的水解动态及其在自然水体中的降解特性

农药的降解特性是评价其环境安全性的重要指标。为评价植物源农药苦参碱对水环境的安全性,依据“化学农药环境安全性评价试验准则”,采用室内模拟试验探讨了苦参碱的水解动态及其在自然水体中的降解特性和影响因素。结果表明:苦参碱在不同pH值缓冲液中水解均较缓慢,120 d后水解率仍低于25%,属于难降解型;其在6种自然水体中降解均较快,半衰期在6.3~12.8 d之间,降解速率排序依次为池塘水河水雨水湖水海水自来水;在6种自然水体中（25℃±1℃）,苦参碱降解速率随其初始浓度的升高而减慢,半衰期与初始浓度呈正相关,但均小于30 d,属于易降解型。比对试验表明:微生物是影响苦参碱降解速率的主要因素,水体中微生物的量与其降解半衰期呈显著负相关关系（P=0.006）。可见,苦参碱在自然水体中易降解,该特性对于指导苦参碱的实际应用具有重要意义。     

Methyl bromide and PCNB for sclerotium crown rot control in iris

Methyl bromide (MB) at rates of 500, 1000 and 1500 kg/ha, Terraclor 75 WP (PCNB) at 150 and 300 kg/ha, and combinations of the two, were studied for control ofSclerotium rolfsii prior to iris cultivation. Sclerotia buried 10 cm deep in soil were all killed by MB at 500 kg/ha; at greater depths higher doses were required. Bulbs harvested from PCNB- and PCNB + MB-treated plots were healthy; 75% of the bulbs in control plots were infected at harvest. When MB was used alone, the soil became re-infested (2–6% diseased plants). Bromide toxicity, correlated with the MB dose applied, appeared 41/2 months after planting; leaves yellowed and senesced prematurely. MB treatments also reduced bulb size, and residual phytotoxicity was found when the bulbs from treated plots were planted in the following year.     

Persistence of chlorfenvinphos in natural waters

Chlorfenvinphos was sprayed at a dosage level of 74 kg/ha (some 20–40 times the normal rate of application to agricultural land) on to the surface of a pond so that the water contained an average concentration of 6.1 ppm. This decreased to 2.0 ppm after five hours, and to 0.12 ppm after 1 month. Residues were detected in the mud 5 hours after the treatment of the water and the concentration increased rapidly up to 5 hours after treatment and reached a maximum value of 0.32 ppm at 115 hours after treatment. Chlorfenvinphos persisted in mud for at least 34 days and whilst there was a decrease in the numbers of Chironomidae larvae the numbers of other animals were too small to detect any significant changes. It seems unlikely that contamination of ponds by aerial spraying at commercial dosages (up to 5 kg/ha) or from run-off and leaching of chlorfenvinphos from treated soil would be a serious hazard to free swimming aquatic animals.     

溴甲烷熏蒸处理鲜切花及其害虫的试验

使用溴甲烷对16种切花及主要携带的南美斑潜蝇、棉蚜、二斑叶螨及花蓟马等害虫进行熏蒸试验。结果表明：如仅带有蚜虫或蓟马，所有供试切花均可进行熏蒸处理；如带有叶螨或斑潜蝇，金鱼草、菊花和孔雀草不宜熏蒸，玫瑰、勿忘我、康乃馨、百合、马蹄莲、情人草、非洲菊、剑兰和石斛兰可以熏蒸，满天星、天堂鸟、橙菠萝和紫罗兰在21℃下以36g/m^3，1．5h处理，对品质有轻度影响，但可100％杀死叶螨及斑潜蝇的成虫、幼虫和蛹。由于斑潜蝇卵的耐药性比其它虫态要强，对带有斑潜蝇卵而耐药性较差的切花，可以在采收后于室温下放置1～3天，待卵孵化后再进行熏蒸处理。     

竹绿虎天牛溴甲烷熏蒸处理技术研究

1985～2005年,美国报道从我国出口的竹制品中发现包括竹绿虎天牛(Chlorophorus annularis F.)在内的20多种有检疫意义的害虫.由于目前还没有针对竹制品中竹绿虎天牛的熏蒸处理技术指标,美国APHIS-PPQ采用其检疫处理手册的T404-d方案对竹制品进行熏蒸处理,即溴甲烷熏蒸24h.美国采用的竹制品熏蒸方案中溴甲烷的用量较高,本文应用比T404～d方案更低剂量的溴甲烷,研究竹桩中竹绿虎天牛的熏蒸效果.溴甲烷熏蒸试验在自制的小型熏蒸箱中进行,在26.7℃48 g/m3、21.1℃ 64 g/m3、15.6℃ 80 g/m3、10.0℃ 96 g/m3和4.4℃ 112 g/m3等5个温度和剂量组合,共20个试验(每个剂量4个重复)共熏蒸处理2847头幼虫、140头蛹和122头成虫,死亡率达100%,而在3组对照中共发现455头活虫.同时,用装满竹杆(80%)的20尺集装箱模拟竹制品出口熏蒸试验,以检查在24h的熏蒸过程中溴甲烷是否保持必需的浓度要求.本研究推荐了较低剂量的溴甲烷熏蒸处理竹制品的新的技术指标.     

Pesticide residues in foodstuffs in England and Wales. Part II: Inorganic bromide ion in cucumber,tomato and self-blanching celery grown in soil fumigated with bromomethane,and the ‘natural’ bromide ion content in a range of fresh fruit and vegetables

Surveys of inorganic bromide ion residues in tomatoes, cucumbers and selfblanching celery, commercially produced in England following soil sterilisation with bromomethane, have been carried out since 1979. The mean bromide ion level in 29 late-season cucumber samples was approximately 28 mg kg⁻¹ and ranged up to 109 mg kg⁻¹. Analysis of 242 tomato samples gave estimated mean bromide ion levels per plant ranging from 6 to 187 mg kg⁻¹ in fruit picked throughout the season from seven holdings, on six of which bromomethane had been used fairly recently prior to planting. A statistically significant fall in bromide levels over the growing season was shown on four of the sites. In 38 samples of self-blanching celery, the mean bromide ion level was 104 mg kg⁻¹ even though the mean interval between fumigation and planting was in excess of 1 year. Retail surveillance indicated that a large number of crops are likely to have bromide ion levels below 10mg kg⁻¹.     

木质包装集装箱溴甲烷检疫熏蒸技术研究

对集装箱装运的出口货物木质包装进行了溴甲烷熏蒸试验 ,结果说明 ,当环境温度为 2～ 1 6℃时 ,采用溴甲烷投药剂量 80 g/m3 ,熏蒸 2 4h能够全部杀死黄斑星天牛幼虫 ,其CT值为 1 1 2 5 8～ 3345 3g h/m3 ;环境温度为 5～ 2 0℃时 ,采用 6 4g/m3 投药剂量 ,同样熏蒸 2 4h ,CT值为 1 2 1 0 8～ 1 51 0 8g h/m3 ,黄斑星天牛幼虫同样全部死亡。溴甲烷汽化后直接从集装箱门上部投药能够使药剂分布均匀。熏蒸结束后通风散气 2 4h ,集装箱到达美国后其内部溴甲烷残留气体浓度低于 5× 1 0 -6。     

樱桃中苹果蠹蛾溴甲烷熏蒸试验研究

试验设11~15℃、16~20℃、21~26℃3个温度区间,试验用苹果蠹蛾幼虫人工接种到樱桃上,分别用4种不同溴甲烷剂量进行处理,每个处理设5个重复,1个对照,试验在温控室的熏蒸桶中进行。结果表明,在11~15℃,溴甲烷剂量48 g/m3,熏蒸2h;16~20℃,溴甲烷剂量40 g/m3,熏蒸2h;21~26℃,溴甲烷剂量32g/m3,熏蒸2h,均能够100%杀死樱桃中苹果蠹蛾幼虫。考虑温度对樱桃品质的影响,建议将11~15℃、溴甲烷剂量48g/m3,熏蒸2h,作为溴甲烷熏蒸樱桃中苹果蠹蛾的技术参数。     

Development and validation of residue methods for the determination of the pyrethroids lambda-cyhalothrin and cypermethrin in natural waters

This paper describes the development of methods suitable for the sampling and analysis of the pyrethroid insecticides lambda-cyhalothrin and cypermethrin in natural waters. A solid-phase water-sampling method which avoids the requirement for transport and storage of large volumes of water is described. This method is shown to be capable of extracting trace levels (ng litre^?-1) of the title compounds from natural waters with efficiencies of at least 80%. Chromatographic analysis of processed samples by gas chromatography–electron capture detection enables determination of residues at levels of 1–2 ng litre^?-1 in water.     

Variation in chlorotoluron photodegradation rates as a result of seasonal changes in the composition of natural waters

BACKGROUND: It is important to understand the degradation of organic molecules in surface waters to ensure that risk assessments, intended to prevent adverse effects on human health and the environment, are robust. One important degradation mechanism in surface waters is photodegradation. This process is generally studied in laboratory test systems, and the significance of the results is then extrapolated to the field. The aim of this work was to assess how fluctuations in the composition of surface water influence the photodegradation rate of chlorotoluron. RESULTS: Photodegradation DT₅₀ values in the lake (mean = 26.0 days) and pond (mean = 26.0 days) were significantly slower than in the river (mean = 6.8 days) and stream (mean = 7.3 days) samples. The DT₅₀ values in the pond and lake samples were similar to the direct photolysis value (mean = 28.6 days). Photodegradation was significantly faster in the stream and river samples, suggesting that indirect photolysis was significant in those waters. Principal component analysis indicated a strong inverse correlation between nitrate concentration and degradation rate. CONCLUSIONS: Nitrate concentration had a strong influence on the rate of photodegradation, with increasing nitrate concentrations sharply reducing the DT₅₀. However, this effect was restricted to a narrow concentration range and levelled off quite quickly, such that further increases in the nitrate concentration had no significant effect on the rate of degradation. Extrapolating photodegradation rates of chlorotoluron from the laboratory to the field should be relatively straightforward, provided the nitrate concentrations in the waters are known. Copyright © 2012 Society of Chemical Industry     

黑河中游西墩滩荒漠植物生长对水分变化响应研究

土地荒漠化是当前十大环境问题之一,对人类的生存和发展构成了严重威胁。为了分析荒漠化防治中植物生长与水分变化的关系,在黑河流域中游荒漠区建立试验站长期定位监测,已取得了土壤水、地下水、降水等水分数据和生物量、盖度等植物生长数据,并采用特征参数算法、相关和多元回归方法,分析了植物生长和水分的年内、年际变化特征及相关回归模型。结果表明:1)2006-2014年际变化上,土壤水和降水变化较剧烈,地下水位变化较缓和。植物盖度变化呈波动性略有增大趋势,而生物量、降水、土壤水、地下水位变化呈波动性略有降低趋势,但变化都不明显。2)在植物生长季的3-11月份期间,土壤各层含水率变化步调基本一致,植物平均生物量和盖度变化步调基本一致,降水量、地下水埋深变化步调基本一致,年内变化幅度从大到小依次为降水>地下水位>土壤水>生物量>盖度。3)植物平均生物量与平均盖度、地下水埋深、降水量的回归模型为B=1.895C-0.033D+0.834P+44.369(R~2=0.796,P<005),通过模型可预测生物量变差的79.6%,准确率可达67.4%。本研究可为荒漠化防治中的水资源管理以及退耕还林、天然林保护、黑河流域综合治理等工程对水资源影响的评估等提供科技支撑和参考数据。     

Hydrolysis and photolysis of flumioxazin in aqueous buffer solutions

To determine the degradation rates and degradation products of the herbicide flumioxazin in aqueous buffer solutions (pH 5, 7 and 9), its hydrolysis and photolysis were investigated at 30 degrees C in the dark, and in a growth chamber fitted with fluorescent lamps simulating the UV output of sunlight. The rate of hydrolysis of flumioxazin was accelerated by increasing pH. The t(1/2) values at pH 5, 7 and 9 were 16.4, 9.1 and 0.25 h, respectively. Two degradation products were detected and their structural assignments were made on the basis of LC-MS data. Degradation product I was detected in all buffer solutions while degradation product II was detected in acidic buffer only. Both degradation products appeared to be stable to further hydrolysis. After correcting for the effects of hydrolysis, the photolytic degradation rate also increased as a function of pH and was approximately 10 times higher at pH 7 than that at pH 5, showing t(1/2) values of 4.9 and 41.5 h, respectively. Degradation products formed by photolysis were the same as those formed by hydrolysis. Flumioxazin was degraded more extensively at high pH and should degrade in surface water.     

Residues in apples and sweet cherries after methyl bromide fumigation

Methyl bromide fumigations are used to treat apples, Malus domestica Borkh, and sweet cherries, Prunus avium (L), before export to Japan. In order to expand existing markets, additional cultivars are being prepared for export to Japan. As part of the approval process, residue analyses must be conducted and residues must be at acceptable levels. Five apple cultivars (‘Braeburn,’ ‘Fuji,’ ‘Gala,’ ‘Jonagold,’ and ‘Granny Smith’) were fumigated at 40 g m⁻³ for 2 h at 10 °C, and six sweet cherry cultivars (‘Brooks,’ ‘Garnet,’ ‘Lapin,’ ‘Rainier,’ ‘Sweetheart,’ and ‘Tulare’) were fumigated for 2 h with 64 g m⁻³ at 6 °C, 48 g m⁻³ at 12 °C, 40 g m⁻³ at 17 °C, and 32 g m⁻³ at 22 °C. Three replicates of fruit from each fumigation were analyzed for methyl bromide and bromide ion residues periodically with time. Methyl bromide residues for both apples and cherries were the highest immediately after fumigation, but rapidly declined so that only ‘Braeburn’ had residues >8 µg kg⁻¹ after 13 days and, except for ‘Lapin,’ all cherries were <1 µg kg⁻¹ after seven days. Average bromide ion residues were between 3.3 and 4.9 mg kg⁻¹ among apple cultivars, and between 3.7 and 8.0 µg kg⁻¹ among cherry cultivars. Published in 2000 for SCI by John Wiley & Sons, Ltd     

Studies of plant cuticle and spray droplet interactions: A fresh approach

The effects of cuticular properties on the impaction and redistribution of aqueous and oil solutions, emulsions and wettable powders were studied using a microapplicator, which dispensed monosize droplets (50-400 μm), and a range of techniques including scanning electron microscopy, X-ray analysis and microautoradiography. Lateral and transcuticular movement of active ingredients was monitored by stripping the outermost wax layers and adhering deposits with cellulose acetate films applied as a spray from an acetone solution. Spread factors, determined using fluorescent markers and a reflectance microscope, varied extensively. Oil formulations spread rapidly through layers of crystalline wax whereas aqueous solutions distributed most readily over smooth surfaces. An X-ray analyser attachment to the scanning electron microscope proved particularly useful for investigating the complex interactions occurring between plant surfaces and diluted e. c. and w. p. formulations. K^amaps and elemental spectra confirmed that lipophilic materials partitioned preferentially into the organic phase which separated as a zone at the outer edge of the droplet residue, whereas water-soluble compounds concentrated in the central region.     

Facilitating trade in fresh fruits and vegetables by developing disinfestation protocols: a case study

The export of horticultural produce, especially fresh fruits and vegetables, has been on the increase in India. There is an increased realization and implementation of pre- and post-harvest pest management practices, leading to increased production, quality and shelf life while meeting WTO requirements. Several countries prohibit imports from India owing to the presence of quarantine pests, particularly commodities that are host plants of Bactrocera dorsalis and Bactrocera cucurbitae . However, once a complete disinfestation technique has been established and approved, importation can be permitted. In the past, specific imports of fresh fruits have already been allowed on the basis of agreed treatments. Appropriate disinfestation protocols for other fresh fruits are currently being developed in India, particularly with respect to fruit flies, to allow prohibitions of export to Japan and other countries to be lifted.     

The absorption of cypermethrin in the grasshopper Melanoplus sanguinipes (Fab.): Effects of volatilisation,temperature, age,sex and parasitisation by Malameba locustae (King and Taylor)

The residues from metered doses of cypermethrin were recovered from excised portions of grasshopper cuticle to determine losses by volatilisation. Residues from similar doses were also recovered from the cuticles of intact grasshoppers and from whole body homogenates after rinsing the cuticle, to determine rates of absorption and losses from metabolism. Residues were recovered from males and females one week and three weeks after fledging in grasshoppers infected with Malameba locustae and in uninfected ones. They were maintained at 15 or 30°C and sampled from each combination of factors at 4, 8, 16, 24, 30 and 48 h after treatment. There was no measurable loss of cypermethrin by volatilisation up to 72 h after application to excised portions of cuticle at either 15 or 30°C. In all combinations of factors, more cypermethrin was recovered externally (P <0.05) from grasshoppers held at 15°C than those held at 30°C and more from infected grasshoppers than from those that were uninfected. Significantly more cypermethrin was also recovered externally from males than from females (P <0.05) and more from infected one-week-old grasshoppers than those that were three weeks old. At 15°C there was a gradual trend towards accumulation of cypermethrin internally, but at 30°C an initial trend towards accumulation was followed by one of decline. Residual cypermethrin recovered could in general be related to the negative temperature coefficient of toxicity, to a decreased sensitivity to cypermethrin in infected grasshoppers and to an increased sensitivity in older grasshoppers.     

Hydrolysis of cyanazine and related diaminochloro-1,3,5- triazines. Part II: hydrolysis in sulphuric acid solutions

Hydrolysis of cyanazine in sulphuric acid solutions involves primary attack at the nitrile group to give first the corresponding amide and then the carboxylic acid followed subsequently by displacement of the chlorine atom. Comparison of the respective reaction rates showed that, in sulphuric acid solutions (at concentrations around 0.5_M) at 25°C, the rate of this attack at the nitrile group is approximately ten times faster than at the chlorine atom. The kinetic data indicate that in these moderately acid solutions the mechanism of cyanazine hydrolysis corresponds to an A-2 reaction involving prior protonation of the nitrile group followed by rate determining nucleophilic attack by water. However, at higher acidities, the rates decelerate which leads both to diversion from the Zucker-Hammett postulate for simple A-2 reactions and to undue curvature in the Bunnett or Bunnett-Olsen linear free-energy plots, so that with the present data such a conclusion cannot be extended to the reaction in solutions of acidity higher than 0.5_M. Removal of the chlorine atom attached to the 1,3,5-triazine ring in atrazine was also found to be an A-2 reaction in moderately acid solutions, but at higher acidities ([H⁺]>2_M), there is an acceleration in the rate. It is suggested that this is a consequence of diprotonation of the diamino-1,3,5-triazine molecule.