Identification of the dimethylbenzyl mercapturic acid in urine of rats administered with 1,2,4-trimethylbenzene

A study was undertaken of the mercapturic acid metabolism of 1,2,4-trimethylbenzene in the rat. Of three regioisomeric dimethylbenzyl mercapturic acids, i.e. 2,4-, 2,5- and 3,4-dimethylbenzyl isomers, the third isomer was not found in the urinary mercapturic acid isolated by preparative HPLC, from the comparison of NMR spectrum of the isolate with those of authentic specimens. The urinary mercapturate was then assigned to 2,4- and/or 2,5-dimethylbenzyl isomers. The excretion rate of the mercapturic acid was 14-20% of dose as 2,4-dimethylbenzyl isomer.     

Identification of the dimethylbenzyl mercapturic acid in urine of rats treated with 1,2,3-trimethylbenzene.

The structure was investigated of the mercapturic acid excreted in urine of rats after the i.p. administration of 1,2,3-trimethylbenzene. Of the two regioisomeric mercapturic acids, i.e. N-acetyl-S-(2,3-dimethylbenzyl)-L-cysteine and N-acetyl-S-(2,6-dimethyl-benzyl)-L-cysteine, only the former was isolated by preparative HPLC and identified, by comparison with an authentic specimen. The excretion rate of the mercapturate was estimated to be approximately 5% of dose, not a substantial metabolic route.     

Metabolism of 2‐chloro‐N‐isopropylacetanilide (propachlor) in the sheep and milk goat

Abstract

Sheep metabolized a single oral dose of 2‐chloro‐N‐isopro‐pylacetanilide (propachlor) to four urinary metabolites. These were 2‐(S‐cysteinyl)‐N‐isopropylacetanilide and 2‐[S‐(N‐acetyl) cysteinyl]‐N‐isopropylacetanilide and the glucuronide conjugates of 4'‐hydroxy‐N‐isopropyl‐2‐methylsulfonylacetanilide and N‐(1‐hydroxyisopropyl)‐2‐methylsulfonylacetanilide. Residues (ppb equivalents of propachlor) from [¹⁴C]‐propachlor in the milk from a goat given daily oral doses (1.3 mg of propachlor three times daily for 15 days) plateaued at about 2 to 4 ppb equivalents of propachlor. In goat tissue, residues ranged from 1 ppb (fat) to 20 ppb (liver). Fecal and tissue metabolites were not identified.     

Synthesis, characterization and chromatographic separation of tetrachlorobenzene-related compounds

Sulphoxide, sulphone and mercapturic acid derivatives of isomeric tetrachlorobenzene were synthesized. These compounds and isomers of tetrachlorophenol were characterized by spectroscopic and chromatographic methods.     

Studies on the origin of the methylsulfonyl‐containing metabolites from propachlor

Abstract

Metabolites in which the chlorine from propachlor has been replaced by a cysteine group or a methylsulfonyl group [‐S(O₂) CH₃] are present in the urine of rats dosed orally with propachlor. In the present study, urine from rats given single oral doses of ³⁵S‐labeled cysteine conjugate of propachlor contained metabolites having the methylsulfonyl groups labeled with S. No metabolites containing ¹⁴C‐labeled methylsulfonyl groups were isolated from urine of rats given single oral doses of the cysteine conjugate of propachlor in which the cysteine group was uniformly labeled with ¹⁴C. These findings show that the cysteine conjugate of propachlor is the source of sulfur in the methylsulfonyl‐containing metabolites. Therefore, we suggest that a C‐S lyase present in the animal cleaves the cysteine conjugate of propachlor and thus allows further metabolism of the sulfur to a methylsulfonyl moiety.     

N-acetyl-S-(pentachlorophenyl)cysteine,a new urinary metabolite of hexachlorobenzene

The present paper describes the isolation and identification of a new metabolite of hexachlorobenzene (HCB), which is N-acetyl-S-(pentachlorophenyl)cysteine (PCC), frequently named pentachlorophenylmercapturic acid or 2-acetamido-3-(pentachlorophenylmercapto)propionic acid. PCC has been detected in and identified from rat urine. The syntheses of PCC and the isomeric tetrachlorophenylmercapturic acids (TCC) are described in the following paper.     

Metabolism of bis-methylthiotetrachlorobenzene in rats

Oral doses of bis-methylthiotetrachlorobenzene (bis-MTTCB) given to control rats and rats with cannulated bile ducts showed that at least 50% of the dose, although excreted mainly as bis-MTTCB in the feces, was metabolized. The metabolism involved replacement of one of the methylthio groups with glutathione, biliary excretion of the mercapturic acid pathway metabolites, and subsequent reformation of bis-MTTCB which is excreted with the feces.     

煤基腐殖酸对外源砷胁迫下玉米生长及生理性状的影响简

为了筛选用于砷污染土壤治理的煤基腐殖酸，采用盆栽实验研究了施用不同种类和浓度的煤基腐殖酸及EDTA对外源砷胁迫下玉米株高、株鲜重、株干重、根干重、砷积累量、叶片抗氧化酶（POD，SOD和CAT）活性和脯氨酸含量的影响。结果表明，11种供试煤基腐殖酸均促进了玉米生长，提高了叶片POD、SOD和CAT活性。其中6和10号腐殖酸可降低土壤砷活性和显著抑制玉米吸收和积累砷，而8和9号腐殖酸增加了土壤活性砷和显著促进了玉米对砷的吸收和累积，且不同程度地强于EDTA。除8和9号外，其余腐殖酸均可明显降低玉米叶片脯氨酸的含量。EDTA可显著促进玉米吸收和积累砷，且加剧了砷对玉米的危害。因此，8和9号供试煤基腐殖酸可以替代EDTA活化土壤砷，与植物配合以提高砷污染土壤的植物修复速度和效果，而6和10号供试煤基腐殖酸则可用于土壤砷钝化剂，以保证作物产品的安全。     

煤基腐殖酸对外源砷胁迫下玉米生长及生理性状的影响

为了筛选用于砷污染土壤治理的煤基腐殖酸，采用盆栽实验研究了施用不同种类和浓度的煤基腐殖酸及EDTA对外源砷胁迫下玉米株高、株鲜重、株干重、根干重、砷积累量、叶片抗氧化酶（POD，SOD和CAT）活性和脯氨酸含量的影响。结果表明，11种供试煤基腐殖酸均促进了玉米生长，提高了叶片POD、SOD和CAT活性。其中6和10号腐殖酸可降低土壤砷活性和显著抑制玉米吸收和积累砷，而8和9号腐殖酸增加了土壤活性砷和显著促进了玉米对砷的吸收和累积，且不同程度地强于EDTA。除8和9号外，其余腐殖酸均可明显降低玉米叶片脯氨酸的含量。EDTA可显著促进玉米吸收和积累砷，且加剧了砷对玉米的危害。因此，8和9号供试煤基腐殖酸可以替代EDTA活化土壤砷，与植物配合以提高砷污染土壤的植物修复速度和效果，而6和10号供试煤基腐殖酸则可用于土壤砷钝化剂，以保证作物产品的安全。     

Metabolism of 2-chloro-N-isopropylacetanilide in chickens

2-Chloro- -isopropylacetanilide was quantitatively metabolized in chickens in the mercapturic acid pathway (MAP). The MAP metabolites (cysteine conjugate, -carboxymethyl- -acetyl cysteine, -acetyl cysteine conjugate, and -acetyl cysteine sulfoxide conjugate) were excreted mainly with the urine with minor amounts (less than 7% of the dose) excreted with bile. The cysteine conjugate was precursor for all the MAP metabolites, as well as, for -isopropyloxanilic acid and -isopropylacetanilide. Cysteine conjugate β-lyase activity was detected in the intestinal contents in vitro but was not manifested in vivo when the cysteine conjugate was injected intracecally.     

污水中溶解游离氨基酸和结合氨基酸测定方法研究

采用邻苯二甲醛作为柱前衍生化试剂，结合反相高效液相色谱，对污水中溶解游离氨基酸（dissolvedfreeami．nOacid，DFAA）进行定性和定量分析，探讨了污水样品有无前处理对DFAA分析的影响，并采用气相酸水解方法对污水中总溶解氨基酸（dissolvedtotalaminoacid，DTAA）进行了分析。结果表明，污水经过pH调节和N，流清洗后，可以明显去除氨和挥发性胺的干扰，色谱峰更加清晰；前处理后的水样经RP—HPLC分析，能够快速检测出14种氨基酸，各氨基酸在一定线性范围内呈现良好的线性关系，相应的线性相关系数（R^2）均大于0．99，加标回收率为92％～102％。污水处理厂进水和出水中氨基酸主要以溶解结合氨基酸（dissolvedcombinedaminoacid，DCAA）为主，与进水相比，出水中DFAA含量减少了0．22μmol／L，DTAA由5．68μmol／L降至3．08μmol／L。     

Acute toxicity of aromatic and non-aromatic fractions of naphthenic acids extracted from oil sands process-affected water to larval zebrafish

The toxicity of oil sands process-affected water (OSPW) has regularly been attributed to naphthenic acids, which exist in complex mixtures. If on remediation treatment (e.g., ozonation) or on entering the environment, the mixtures of these acids all behave in the same way, then they can be studied as a whole. If, however, some acids are resistant to change, whilst others are not, or are less resistant, it is important to establish which sub-classes of acids are the most toxic.     

Characterization of humic substances of different origin by means of mass spectrometry and neural networks

Mass spectrometry fingerprinting of humic acids extracted from different soils has been carried out using laser desorption/ionization mass spectrometry (LDI-TOF MS). LDI-TOF MS provides characteristic mass spectra fingerprints for the humic acids of different origin. The information given in the fingerprints was evaluated for natural grouping trends in the samples by neural networks computing tools, such as self-organizing feature map (SOFM). This approach is efficient for recognizing patterns in the humic acids samples independently of their characteristic variability; variability characterizing natural products such as humic substances. The use of multi-layer perceptron artificial neural networks gave a successful classification of the samples.     

重金属离子在腐植酸上吸附的研究

对4种代表性重金属离子在腐植酸上吸附、pH对竞争吸附的影响及其吸附机理进行了研究。结果表明，Cu2＋、Pb2＋、Zn2＋的吸附等温线为F型，而Cd2＋等温线为L型；2．5＜pH＜3．5时，竞争吸咐次序为Cu2＋＞Pb2＋＞Cd2＋＞Zn2＋；pH＞5．0时，Cd2＋＞Cu2＋＞Zn2＋＞Pb2＋；Cu2＋在腐植酸上的吸附主要是以与腐植酸形成配合物的方式相互结合。     

食品废弃物厌氧消化产乙酸的研究

通过实验,研究了pH、总固体浓度(TS)、碳氮比(C/N)对食品废弃物厌氧消化产乙酸的影响,详细考察了挥发性脂肪酸(VFA)的组成和浓度及乙酸浓度随时间的变化规律.结果表明,pH为6.5、TS为7%(质量分数)、C/N为16:1时,总VFA的最大质量浓度为31.56 g/L,乙酸的最大质量浓度为19.46 g/L.     

茅草添加与温度变化对餐厨垃圾厌氧水解产酸的影响

比较了茅草添加在温度变化条件下对餐厨垃圾厌氧水解过程小分子有机酸产量的影响，提出一种新型餐厨垃圾的资源化方式。研究结果显示，餐厨垃圾在55℃条件下厌氧水解主要产物为乳酸，达到25．7g／L，其干物质转化率可以达到32．1％（gTS），而餐厨＋茅草处理在同样条件下的乳酸产量为20．1g／L，干物质转化率为25．1％。温度下降为37℃后继续进行的的厌氧水解，得到的主要产物是乙酸、丙酸和丁酸，餐厨处理和餐厨＋茅草处理这两者的峰值分别为6．5、2．8、8．0和6．1g／L、2．7g／L和5．9g／L。结果显示茅草添加可以在一定程度上调节水解产物的比例，而温度变化可以调控小分子有机酸的产量。本研究结果表明，厌氧水解是一种有潜力的小分子有机酸生产与餐厨垃圾资源化处理途径。     

酸碱联合调节剩余污泥过程中氮、磷和有机质的释放

实现城市污泥的减量化和资源化是污水厂面临的难题之一。通过采用(1)先酸性(pH=3)后碱性(pH=10)、(2)先碱性(pH=10)后酸性(pH=3)的两段控制方式(每段反应8 d),同时做pH不调的对比实验,研究剩余污泥水解酸化过程中氨氮、磷酸盐和溶解性COD(SCOD)、碳水化合物、蛋白质和挥发性脂肪酸(VFAs)等有机质组分的释放。结果表明,酸碱联合调节有利于各组分的释放;氮和磷在酸性条件下的释放量大于碱性,有机质在碱性条件下的释放量大于酸性;采用(2)方式,调为酸性后反应1 d,氨氮的释放量即达到最大(17.28 mg/g TS);采用(1)的调节方式反应7 d,磷酸盐能达到最佳释放量(14.16 mg/g TS);总VFAs的产生受反应时间的影响较大,其余有机质组分在(2)的调节方式下,6 d左右即可达到较大释放量。     

Determination of C(5)-C(12) perfluoroalkyl carboxylic acids in river water samples in the Czech Republic by GC-MS after SPE preconcentration

A method employing solid phase extraction followed by gas chromatography-mass spectrometry with negative chemical ionization has been developed for determination of ultratrace concentrations of perfluoroalkyl carboxylic acids in river water. The effects of the experimental parameters, such as the pH, additions of NaCl and an ion-pairing agent (tetraethylammonium bromide) and the kind of the elution agent, on the efficiency of the test acid extraction have been studied. The analyte extraction recoveries and the limits of detection and determination have been found. The method developed has been tested on determinations of perfluoroalkyl carboxylic acids in the waters of the two largest Czech rivers, Vltava and Labe (Elbe). The best extraction results have been attained without any alteration of the sample pH, with an addition of tetrabutylammonium bromide (a concentration of 50 μg mL⁻¹ in the sample) and using methanol as the elution agent. Under these conditions, the recoveries of the test acids in the spiked real samples are within ranges from 60% to 104% and 53% to 111% for analyte concentration levels of 1.40 ng mL⁻¹ and 0.14 ng mL⁻¹, respectively, depending on the lengths of the perfluorinated chains of the acids. In general, the recovery decreases with increasing length of this chain. The method developed exhibits very low limits of detection and determination and the results are fully comparable with those obtained when using more expensive HPLC-MS/MS instrumentation. Typical values amount to tenths to tens of pg mL⁻¹ and units to one hundred pg mL⁻¹ for the limits of detection and determination, respectively; the measuring sensitivity increases with increasing length of the analyte chain. The analyzes of real samples from the Vltava and Elbe rivers have demonstrated that the results obtained are similar to the values published for contamination of the Elbe and other rivers in western and central Europe. The concentrations determined are of the order of units to tens of pg mL⁻¹ and the C₈-C₁₀ acids occur most often.     

水环境中腐殖酸的荷电特性与聚集特性

通过腐殖酸的Zeta电位和粒径的变化规律研究,探讨化学条件对腐殖酸的荷电状态和聚集状态的影响。结果表明,腐殖酸具有自我凝聚的特性;在pH较低和溶液离子强度较高时,腐殖酸胶粒的Zeta电位绝对值减小而聚合度增大,从而使腐殖酸胶粒聚集而凝聚;随腐殖酸浓度增大,腐殖酸胶粒的Zeta电位绝对值增大,腐殖酸胶粒的缩聚程度降低而使粒径减小。     

Photosensitized degradation of caffeine: role of fulvic acids and nitrate

The photolysis of caffeine was studied in solutions of fulvic acid isolated from Suwannee River, GA (SRFA) and Old Woman Creek Natural Estuarine Research Reserve, OH (OWCFA) with different chemical amendments (nitrate and iron). Caffeine degrades slowly by direct photolysis (>170 h in artificial sunlight), but we observed enhanced photodegradation in waters containing the fulvic acids. At higher initial concentrations (10 μM) the indirect photolysis of caffeine occurs predominantly through reaction with the hydroxyl radical (OH) generated by irradiated fulvic acids. Both rate constant estimates based upon measured OH steady-state concentrations and quenching studies using isopropanol corroborate the importance of this pathway. Further, OH generated by irradiated nitrate at concentrations present in wastewater effluent plays an important role as a photosensitizer even in the presence of fulvic acids, while the photo-Fenton pathway does not at neutral or higher pH. At lower initial concentrations (0.1 μM) caffeine photolysis reactions proceed even more quickly in fulvic acid solutions and are influenced by both short- and long-lived reactive species. Studies conducted under suboxic conditions suggest that an oxygen dependent long-lived radical e.g., peroxyl radicals plays an important role in the degradation of caffeine at lower initial concentration.