Metabolism of 14C‐carbaryl and 14C‐1‐naphthol in moist and flooded soils

Abstract

The metabolism of ¹⁴C‐carbaryl and ¹⁴C‐1‐naphthol in moist and flooded soils was studied in a continuous flow‐through system over a period of 28 days permitting ¹⁴C‐mass balance. The percent distribution of radiocarbon in organic volatiles, carbon dioxide, extractable and non‐extractable (bound) fractions of soils were determined. Organic volatiles could not be detected in both carbaryl and 1‐naphthol treated soils. More of ¹⁴CO₂ (25.6%) was evolved from moist than flooded soil (15.1%) treated with carbaryl. However, the mineralization of ¹⁴C‐1‐naphthol was negligible. The extractable radiocarbon was more in flooded soil (28.9%) than moist soil (5.5%) from carbaryl treatment. Less than one percent was present as parent compound, whereas carbaryl was mainly metabolized to 5‐hydroxy carbaryl in moist soil and to 4‐ and 5‐hydroxy carbaryl in flooded soil. The extractable radiocarbon amounted to 18.2 and 24.3% in moist and flooded soils respectively and the parent compound was less than one percent with 1‐naphthol treatment. Most of the radiocarbon was found as soil bound residues; the formation being more with 1‐naphthol than carbaryl. Humin fraction of the soil organic matter contributed most to soil bound residues of both carbaryl and 1‐naphthol.     

Matrix effects in analysis of dialkyl phosphate metabolites of organophosphate pesticides in urine by gas chromatography/tandem mass spectrometer

Urinary dialkyl phosphate metabolites (DAPs) are used as biomarkers to evaluate human exposure to organophosphate pesticides. The objective was to evaluate potential artifacts in urinary DAPs analysis during sample preparation and method calibration. Diluted urine pools were commonly used to prepare calibration standards to minimize the effects due to the complexity of urine matrix. Matrix effects on measurements of DAPs were evaluated by spiking known amount of standards into distilled water, synthetic urine and diluted urine pool. Different matrices resulted in similar concentrations detected for all target compounds, except dimethylphosphate (DMP) with the deviation of measurement as large as eight times the spiked amount. In this study, we also found that urinary particles, which usually appeared after thawing frozen human urine samples, could affect the measurements of DAPs, especially DMP and diethylthiophosphate (DETP). Results of DAPs measurements in three types of sample matrices, i.e. urine without particles, urine with particles and particles only were compared. DETP could be subject to large error during this preparation step. The use of deuterated and ¹³C₁₂-labeled DAPs as internal standards is also evaluated. Overall, these issues can cause misidentification and inaccuracies, which may significantly affect the data quality.     

Oxidative transformation of polybrominated diphenyl ether congeners (PBDEs) and of hydroxylated PBDEs (OH-PBDEs)

BACKGROUND, AIM, AND SCOPE: The historical and widespread use of polybrominated diphenyl ethers (PBDEs) as flame retardants in consumer products worldwide has caused PBDEs to now be regarded as pervasive environmental contaminants. Most recently, hydroxylated PBDEs (OH-PBDEs) and methoxylated PBDEs (MeO-PBDEs) have emerged as environmentally relevant due to reports of their natural production and metabolism. An important parameter for assessing the environmental impact of a chemical substance is persistence. By formulating the concept that persistence is the result of the substance's physicochemical properties and chemical reactivity, Green and Bergman have proposed a new methodology to determine the inherent persistence of a chemical. If persistence could be predicted by straightforward methods, substances with this quality could be screened out before large-scale production/manufacturing begins. To provide data to implement this concept, we have developed new methodologies to study chemical transformations through photolysis; hydrolysis, substitution, and elimination; and via oxidation. This study has focused on adapting an oxidative reaction method to be applicable to non-water soluble organic pollutants. MATERIALS AND METHODS: PBDEs and one MeO-PBDE were dissolved in tetrahydrofuran/methanol and then diluted in alkaline water. The OH-PBDEs were dissolved in alkaline water prior to reaction. The oxidation degradation reaction was performed at 50 degrees C using potassium permanganate as described elsewhere. The pH was maintained at 7.6 with disodium hydrogen phosphate and barium hydrogen phosphate, the latter also serving as a trapping agent for manganate ions. The oxidation reactions were monitored by high-performance liquid chromatography and reaction rates were calculated. RESULTS: The OH-PBDEs have very fast oxidative transformation rates compared to the PBDEs. The reaction rates seem to be primarily dependent on substitution pattern of the pi-electron-donating bromine substituents and of bromine content. There are indications that further reactions of OH-PBDEs, e.g., methylation to the MeO-PBDEs, decrease the oxidation rates, and thereby generate more persistent substances. DISCUSSION: The resistance of PBDEs to oxidation, a major degradation pathway in air, should be further investigated, since these compounds do undergo long range transport. With slight modifications, the original method has been adapted to include a larger variety of chemical substances, and preliminary data are now available on the oxidative transformation rates for PBDEs and of OH-PBDEs. CONCLUSIONS: The original oxidation degradation method can now include non-water soluble compounds. This modification, using low concentrations of test chemicals, allows us to measure oxidative transformation rates, for some of the lower brominated DEs, data that can be used to assess their persistence in future model calculations. Oxidative transformation rates for PBDEs are slow compared to those for the OH-PBDEs. This suggests that OH-PBDEs, when released into the environment, undergo faster oxidative metabolism and excretion than the PBDEs. RECOMMENDATIONS AND PERSPECTIVES: To evaluate the modified method, more degradation reactions with non-water soluble compounds should be investigated. Recent studies show that OH-PBDEs are present in rats and in humans and, because of their activity as endocrine disruptors, determining their subsequent environmental fate is of importance. The resistance of PBDEs to oxidative degradation should be acknowledged as of possible future concern. Several other compound classes (such as polychlorinated biphenyls (PCBs), hydroxylated polychlorinated biphenyls (OH-PCBs), and pharmaceuticals) need to be subjected to this screening method to increase the database of transformation rates that can be used with this model.     

Metabolism of benzo[a]pyrene in peroxynitrite/Fe(Ⅲ) porphyrin system

The peroxynitrite/porphyrin biomimetic system was established to investigate the effects of peroxynitrite on benzo[a]pyrene (B[a]P) metabolism. Through the comparison of three model systems consisting of different iron porphyrins, we found that the peroxynitrite/T(p-Cl)PPFeCl system showed the highest catalytic efficiency in the metabolism of B[a]P. We analyzed the B[a]P metabolites produced from this system by RP-HPLC method and firstly identified the formation of nitrobenzo[a]pyrenes which are the special metabolites of B[a]P induced by peroxynitrite.     

耐盐类固醇激素降解菌交替赤杆菌MH-B5的降解特性、降解途径及其固定化

从咸水湖中分离得到1株具有类固醇激素降解能力的耐盐菌株,利用16S rRNA基因序列同源性分析确定菌株MH-B5属于交替赤杆菌属(Altererythrobacter),其可生长p H范围为5.5~9.0,可耐受盐度生长范围为0~7%,单碳降解实验表明该菌可以利用雌酮、雌二醇、雌三醇和睾酮.应用超高压液相色谱串联四级杆飞行时间质谱分析得出菌株降解睾酮的过程中主要中间代谢产物为4-雄烯二酮、宝丹酮和雄二烯二酮.应用单一载体和复合载体两种方法分别制备的菌株MH-B5固定化颗粒均可降解雌二醇,批次降解实验表明菌株MH-B5固定化颗粒可有效降解2 mg·L~(-1)雌二醇及其初级代谢产物雌酮.上述研究结果表明菌株MH-B5可在海水中生长良好,其能降解典型雌激素及雄激素睾酮,且经过微生物固定化过程后依然具有类固醇激素的降解特性,因此对类固醇激素污染的咸水环境修复,具有潜在应用前景.     

Isolation and algae-lysing characteristics of the algicidal bacterium B5

Water blooms have become a worldwide environmental problem.Recently,algicidal bacteria have attracted wide attention as possible agents for inhibiting algal water blooms.In this study,one strain of algicidal bacterium B5 was isolated from activated sludge.On the basis of analysis of its physiological characteristics and 16S rDNA gene sequence,it was identified as Bacillusfusiformis.Its algae- lysing characteristics on Microcystis aeruginosa,Chlorella and Scenedesmus were tested.The results showed that:(1)the algicidal bacterium B5 is a Gram-negative bacterium.The 16S rDNA nucleotide sequence homology of strain B5 with 2 strains of B.fusiformis reached 99.86%,so B5 was identified as B.fusiformis;(2)the algal-lysing effects of the algicidal bacterium B5 on M.aeruginosa, Chlorella and Scenedesmus were pronounced.The initial bacterial and algal cell densities strongly influence the removal rates of chlorophyll-α.The greater the initial bacterial cell density,the faster the degradation of chlorophyll-α.The greater the initial algal cell density,the slower the degradation of chlorophyll-α.When the bacterial cell density was 3.6 x l07 cells/ml,nearly 90% of chlorophyll-αwas removed.When the chlorophyll-αconcentration was less than 550μg/L,about 70% was removed;(3)the strain B5 lysed algae by secreting metabolites and these metabolites could bear heat treatment.     

城市污水处理厂污水及污泥中典型药物及其代谢产物的定量检测

基于超声溶剂萃取、固相萃取和超高效液相色谱-质谱联用技术（UPLC-MS/MS）,建立了一种适用于城市污水处理厂污水和污泥中2种典型药物（磺胺甲恶唑和卡马西平）及其5种代谢产物的同步分析方法.污水样品添加硫酸酸化、Na₂EDTA络合金属离子后经固相萃取富集净化;污泥样品通过甲醇/0.2 mol·L^-1柠檬酸溶液（1：1,体积比）超声萃取后经固相萃取富集净化.采用UPLC-MS/MS电喷雾电离源在多反应监测模式下进行目标物的定量分析.结果表明,在优化条件下,7种目标物标准曲线的线性可决系数（R²）均大于0.99,方法回收率为74%~217%,日内与日间相对标准偏差稳定（RSD<20%）,污水定量限为0.17~2.42 ng·L^-1,污泥定量限为0.20~2.85 μg·kg^-1.将该方法成功应用于两家城市污水处理厂样品中,除N-AcSMX外其余6种目标物被检出,其在污水和污泥中的浓度分别为3.92（SMX-DG）~667（LCBZ）ng·L^-1和0.41（2OH-CBZ）~2.74（CBZ）μg·kg^-1.     

6-2氟调醇在活性污泥中的降解

为了解6-2氟调醇(6-2 FTOH)在城市污水处理厂活性污泥中的好氧降解规律,利用室内模拟实验装置,研究了6-2FTOH在未经稀释驯化的活性污泥中的降解动力学及降解产物分布.结果表明,6-2 FTOH能被活性污泥快速吸附并发生降解,降解反应符合一级动力学,半衰期为0.9d.降解产物包括6-2氟调酸(6-2 FTCA)、6-2不饱和氟调酸(6-2 FTUCA)、5-3氟调酸(5-3 FTCA)、5-2s氟调醇(5-2s FTOH)和全氟己酸(PFHxA).第28 d实验结束时,6-2 FTOH残留率为5.5％,6-2 FTCA和6-2 FTUCA的最终产率分别为0和1.2％.5-3FTCA、5-2s FTOH、PFHxA最终产率分别为23.4％、17.6％和1.3％.     

Leaching potential of some phenylureas and their main metabolites through laboratory studies

BACKGROUND, AIMS AND SCOPE: Laboratory studies were conducted with the aim of defining the leaching potential of some phenylureas and their metabolites. A first study was performed for calculating their leaching index (as GUS) on the base of intrinsic properties: persistence (as DT50) and mobility (as Koc) in soil. Another study consisted of aged column leaching experiments whose meaning was to semi-quantify the occurrence of the tested compounds in the leachates, so simulating in field conditions. METHODS: The tested compounds were: diuron, linuron and monolinuron (parents); 3,4-dichloroaniline (DCA), 4-chloroaniline (CLA), 1-(3,4-dichlorophenyl)-3-methylurea (DCPMU), 1-(3,4-dichlorophenyl)urea (DCPU), 1-(4-chlorophenyl)urea (CPU) and monuron, this latter considered both as a metabolite and parent compound. The Koc values of the examined substances were determined by the HPLC screening methods, according to the OECD TG 121. DT50 determinations and aged column leaching experiments were carried out according to SETAC procedures. RESULTS AND DISCUSSION: The examined compounds showed a rather wide range of persistence in soil, with DT50 values less than 2 days for DCA and CLA, close to 8 days for DCPU and CPU and from 16 (diuron) up to 24.8 (DCPMU) days for the others. Their mobility was generally high, based on their Koc values, which ranged from 33 (CPU) to 406 (linuron). The GUS indices indicated that monuron has a clear potential to contaminate groundwater (> 2.8); DCPMU, monolinuron, CPU and diuron are intermediate contaminants (1.8-2.8). Linuron, DCPU, CLA and DCA exhibited a non-leaching behaviour (< 1.8). The aged leaching column experiments showed that parents were found in the leachates at very high percentages respect to the doses applied. The metabolites reached much less percentages, the highest values were observed for monuron from diuron (5.7), CPU (7.2) and DCPMU (8.2%). CONCLUSION: Diuron, Monuron, CPU and DCPMU on the basis of their intrinsic properties, formation from their parents and occurrence in leachates from aged column leaching studies, seem to possess the characteristics of groundwater contaminants. The methodological approach of this study is relatively easy and rapid, hence it can represent a tool for a first screening of compounds such as pesticide metabolites (generally available only in small quantities and for which a field study is not conceivable) or other compounds for which not adequate environmental data are available.     

铜绿假单胞菌降解菲的产物鉴定及代谢过程

研究了1株能快速降解疏水性化合物的铜绿假单胞菌NY3对菲的降解机理。GC-MS分析表明,该菌代谢菲的各个阶段,能够被检测到的主要酸性产物有1-羟基-2-萘甲酸、α-萘酚、邻羟基苯基羰基乙酸、水杨酸、苯甲酸等。铜绿假单胞菌NY3经过一系列氧化代谢将菲转化为1-羟基-2-萘甲酸,进一步反应生成α-萘酚。由菲到1-羟基-2-萘甲酸,未检测到其他产物,说明该阶段产物被继续代谢的速度快,产物含量低不易积累。1-羟基-2-萘甲酸为体系中积累的唯一的主要代谢产物。尽管继续代谢速度慢,但它可以按照α-萘酚、邻羟基苯基羰基乙酸、水杨酸、苯甲酸途径被继续转化。NY3降解菲的代谢产物中未检测到二羟基萘、苯二酚等多羟基化合物,但羟基和羧基处于邻位的化合物,如1-羟基-2-萘甲酸和水杨酸有非常明显积累的趋势,α-萘酚和苯甲酸积累速度次之。