Metabolism of the Nonylphenol Isomer [Ring-U-14c]-4-(3′,5′-Dimethyl-3′-Heptyl)-Phenol by Cell Suspension Cultures of Agrostemma githago and Soybean

Abstract

The biotransformation of the nonylphenol isomer [ring-U-¹⁴C]-4-(3′,5′-dimethyl-3′-heptyl)-phenol (4-353-NP, consisting of two diastereomers) was studied in soybean and Agrostemma githago cell suspension cultures. With the A. githago cells, a batch two-liquid-phase system (medium/n-hexadecane 200:1, v/v) was used, in order to produce higher concentrations and amounts of 4-353-NP metabolites for their identification; 4-353-NP was applied via the n-hexadecane phase. Initial concentrations of [¹⁴C]-4-353-NP were 1 mg L^?1 (soybean), and 5 and 10 mg L^?1 (A. githago). After 2 (soybean) and 7 days (A. githago) of incubation, the applied 4-353-NP was transformed almost completely by both plant species to four types of products: glycosides of parent 4-353-NP, glycosides of primary 4-353-NP metabolites, nonextractable residues and unknown, possibly polymeric materials detected in the media. The latter two products emerged especially in soybean cultures. Portions of primary metabolites amounted to 19–22% (soybean) and 21–42% of applied ¹⁴C (A. githago). After liberation from their glycosides, the primary 4-353-NP metabolites formed by A. githago were isolated by HPLC and examined by GC-EIMS as trimethylsilyl derivatives. In the chromatograms, eight peaks were detected which due to their mass spectra, could be traced back to 4-353-NP. Seven of the compounds were side-chain monohydroxylated 4-353-NP metabolites, while the remaining was a (side-chain) carboxylic acid derivative. Unequivocal identification of the sites of hydroxylation/oxidation of all transformation products was not possible. The main primary metabolites produced by A. githago were supposed to be four diastereomers of 6′-hydroxy-4-353-NP (about 80% of all products identified). It was concluded that plants contribute to the environmental degradation of the xenoestrogen nonylphenol; the toxicological properties of side-chain hydroxylated nonylphenols remain to be examined.     

Electrochemical Monitoring of Methylparathion Degradation in an Acid Aqueous Medium in Presence of Cu(II)

Abstract

A study was undertaken to determine the effect of Cu(II) in degradation of methylparathion (o,o-dimethyl o, 4-nitrophenyl phosphoriotioate) in acid medium. Initial electrochemical characterization of Cu(II) and methylparathion was done in an aqueous medium at a pH range of 2–7. Cu(II) was studied in the presence of different anions and it was observed that its electroactivity depends on pH and is independent of the anion used. Methylparathion had two reduction signals at pH ≤ 6 and only one at pH > 6. The pesticide's transformation kinetic was then studied in the presence of Cu(II) in acid buffered aqueous medium at pH values of 2, 4, and 7. Paranitrophenol appeared as the only electroactive product at all three pH values. The reaction was first order and had k values of 5.2 × 10^?3 s^?1 at pH 2, 5.5 × 10^?3 s^?1 at pH 4 and 9.0 × 10^?3 s^?1 at pH 7. It is concluded that the principal degradation pathway of methylparathion in acid medium is a Cu(II) catalyzed hydrolysis reaction.     

TOTAL ARSENIC ACCUMULATION IN EDIBLE PODS AND SEEDS OF PHASEOLUS VULGARIS

The main objective of this study was to evaluate whether arsenic accumulated in the edible pods and seeds of Phaseolus vulgaris, cv. Helda, above the Spanish maximum recommended concentration for food crops, 1 mg kg^?1 on a fresh weight basis. Only organic arsenicals were used because they are: a) the only arsenic species allowed for agricultural applications and b) more mobile than inorganic species. Selection of French beans, a sensitive plant to arsenic, was based on the fact that arsenic upward translocation is higher in sensitive than in tolerant plants. A 2 × 3 factorial experiment was conducted with two organic arsenic species: methylarsonic acid (MAA) or dimethylarsinic acid (DMAA) and three arsenic concentrations: 0.2, 0.5, or 1.0 mg L^?1. Arsenic phytotoxicity was primarily determined by soluble arsenic concentration. Experimental results showed that the low bean plant tolerance to arsenic is possibly due to the high arsenic upward transport to shoots, which could result in profound negative metabolic consequences. Even under extremely adverse conditions, arsenic residues in edible beans were below the maximum statutory limit set by the Spanish legislation. It can be concluded that the major danger of organic arsenical herbicides is that of decreased productivity rather than high arsenic uptake by consumers.     

Parental phenols exposure and spontaneous abortion in Chinese population residing in the middle and lower reaches of the Yangtze River

Widespread use of phenols has led to ubiquitous exposure to phenols. In experimental animals, phenols increased resorptions, reduced live litter size and fetal body weights. However, there are limited epidemiological evidences of the relationships between exposure to phenols and pregnancy outcomes. We evaluated the associations between parental urinary levels of various phenols and spontaneous abortion in a Chinese population residing in the middle and lower reaches of the Yangtze River. A case-control study was conducted that included 70 case couples with medically unexplained spontaneous abortion and 180 control couples who did not have a history of spontaneous abortion and had at least one living child. Both parental urinary phenols were measured by ultra-high performance liquid chromatography-tandem mass spectrometry including bisphenol A (BPA), benzophenone-3 (BP-3), 2,3,4-trichlorophenol (2,3,4-TCP), pentachlorophenol (PCP), 4-n-octylphenol (4-n-OP) and 4-n-nonylphenol (4-n-NP). Compared with the low exposure group, there was an increased risk of spontaneous abortion with high paternal urinary PCP concentration [odds ratio (OR) = 2.09, 95% Confidence Interval (CI), 1.05–4.14], and maternal exposure to 4-n-OP and alkylphenol(s) also significantly increased the risk of spontaneous abortion (OR = 2.21, 95% CI, 1.02–4.80; OR = 2.81, 95% CI, 1.39–5.65, respectively). Our study firstly provides the evidence that paternal PCP exposure, maternal 4-n-OP and alkylphenol(s) exposure are associated with spontaneous abortion in humans.     

Development and application of LC–APCI–MS method for biomonitoring of animal and human exposure to imidacloprid

Imidacloprid (IMI) is a relatively new neuro-active neonicotinoid insecticide and nowadays one of the largest selling insecticides worldwide. In the present study a LC–APCI–MS based method was developed and validated for the quantification of imidacloprid and its main metabolite 6-chloronicotinic acid (6-CINA) in urine and hair specimens. The method was tested in biomonitoring of intentionally exposed animals and subsequently applied for biomonitoring of Cretan urban and rural population.     

养殖固体废物在硝酸和磷酸溶液中的水解特性

养殖固体废物掺杂磷肥工艺中养殖固体废物与酸的反应直接影响其有机组成。以鸡粪为研究对象,采用L16(45)正交试验研究了鸡粪粒径、酸浓度、鸡粪与酸溶液质量比、反应温度和反应时间对鸡粪在硝酸和磷酸溶液中水解过程的影响。结果表明,硝酸溶液中影响因素显著性依次为鸡粪与硝酸质量比、反应时间、硝酸浓度、鸡粪粒径、反应温度,最优工艺条件为鸡粪粒径0.20mm、硝酸质量分数15%、鸡粪与硝酸质量比0.2∶1.0、反应温度95℃、反应时间4h;在磷酸溶液中影响因素显著性依次为鸡粪与磷酸质量比、反应温度、鸡粪粒径、磷酸浓度、反应时间,鸡粪水解率与反应温度间呈正相关关系,最优工艺条件为鸡粪粒径0.40mm、磷酸质量分数60%、鸡粪与磷酸质量比0.1∶1.0、反应温度95℃、反应时间8h。鸡粪比表面积及其单位质量耗酸量、美拉德反应是制约鸡粪在硝酸和磷酸中水解反应的内因。研究结果为养殖固体废物掺杂有机磷肥的研发和推广提供了理论基础。     

废LCD面板有机材料水热资源化产乙酸

LCD面板主要由附着偏光片及液晶等有机材料的玻璃面板构成。有机材料的去除及资源化利用是废LCD面板处理的第一步。在水热条件下对废LCD面板进行了降解产酸研究。研究考察了反应温度、反应时间、氧化剂用量、水用量及pH值等对水热产乙酸产率及选择性的影响。通过正交实验确定了水热产乙酸的最佳操作条件：反应温度325℃,反应时间5min,氧化剂（30％H2O2）0．6mL,用水量2mL,近中性环境（pH6-6．5去离子水）。此条件下,乙酸产率及选择性分别为68．83％及70．56％。结果表明,以废LCD面板有机材料为原料,采用水热技术进行产乙酸反应,可实现其资源化再利用。     

萃取净化电镀含镉废水

研究了二壬基萘磺酸(DNNSA)形成的微乳液从模拟含镉废水中萃取镉离子的工艺条件。分别考察了相体积比(O/A)、萃取时间、温度及萃取剂浓度对废水中镉离子萃取的影响。结果表明,萃取平衡时间为10 mim,降低温度及增加萃取剂浓度均有利于萃取。紫外光谱证实当DNNSA萃取镉时,所形成萃合物对萘环的结构无影响,且不会破坏微乳相的结构;分子荧光光谱表明镉离子对配体DNNSA有荧光猝灭作用。     

PAFC对水体中持久性有机污染物PFOA的混凝效果

针对含全氟辛酸(PFOA)的工业废水及应对PFOA的污染突发事件,采用PAFC及其复配粘土矿物凹凸棒和沸石进行混凝实验,并对几个影响因素进行了考察。结果表明,在PAFC的最佳投加量10 mg/L时,PFOA和浊度的去除率分别达到70.25%和99.42%,PAFC混凝处理PFOA的效果优于PAC;pH值对PAFC去除PFOA有一定的影响,当pH大于6时有利于PFOA的去除;PFOA和浊度的去除率随原始浊度的增加而增加;活性炭、盐酸改性凹凸棒、盐酸改性沸石、CT-MAB改性的沸石复配PAFC均可提高PFOA的去除率;改性处理后的沸石应用于PFOA的处理中,有望降低处理成本。     

柠檬酸对褐土中DTPA提取态铜、镉含量及对紫花苜蓿吸收铜、镉的影响

为了阐述有机酸对土壤中重金属生物有效性的影响,通过盆栽实验,研究了Cu、Cd复合污染下柠檬酸对褐土中二乙基三胺五乙酸(DTPA)提取态铜和镉含量的影响,并探讨了柠檬酸对植物吸收铜、镉的影响。结果表明,土壤中DT-PA-Cu含量随柠檬酸添加量的增加而减小,添加高浓度铜(Cu 1 000)处理中,DTPA-Cu含量减小更明显。在添加低铜浓度(Cu600)处理下,柠檬酸添加量为2和12 mmol/kg时,土壤DTPA-Cu含量随土壤镉含量的增加而增加,而柠檬酸含量为5mmol/kg时,DTPA-Cu含量在低镉处理(Cd 1)时含量最低。紫花苜蓿中铜含量随柠檬酸添加量的增加明显降低。土壤中DTPA-Cd含量随柠檬酸添加量的增加而减小,且随铜添加量的增加而降低。紫花苜蓿中的镉含量随柠檬酸添加量的增加先增加后减小;在相同柠檬酸添加量处理时,紫花苜蓿中镉的含量随镉含量的增加而增加;在低镉处理下,铜的加入对较低柠檬酸浓度时紫花苜蓿镉含量影响不明显,但柠檬酸浓度为12 mmol/kg时,紫花苜蓿中镉含量随铜添加量的增加而明显增加。