Phytoremediation potential of Spirulina (Arthrospira) platensis: biosorption and toxicity studies of cadmium

This study examines the possibility of using Spirulina (Arthrospira) platensis TISTR 8217 to remove low concentrations of cadmium (less than 100 mg/l) from wastewater. The cyanobacteria were exposed to six different cadmium concentrations for 96 h, and the growth rate was determined using an optical density at 560 nm. The inhibiting concentration (IC50) was estimated using probit analysis. The IC50 at 24, 48, 72, and 96 h were 13.15, 16.68, 17.28, and 18.35 mg/l Cd, respectively. Cellular damage was studied under a light microscope and a transmission electron microscope. Swollen cells and fragmented filaments were observed. Cell injury increased with increasing concentrations of cadmium. Ultrastructural changes were observed in the algae exposed to cadmium concentrations both close to IC50 (14.68 mg/l) and at IC50 (18.35 mg/l). The alterations induced by cadmium were disintegration and disorganization of thylakoid membranes, presence of large intrathylakoidal space, increase of polyphosphate bodies, and cell lysis. In addition, the cadmium adsorption by algal cells was studied. Environmental factors were found to have an effect on biosorption. The uptake of cadmium was not affected by the temperature of the solution, but the sorption was pH dependent. The optimum pH for biosorption of algal cells was 7. The cadmium uptake process was rapid, with 78% of metal sorption completed within 5 min. The sorption data fit well to the Langmuir isotherm. The maximum adsorption capacity for S. platensis was 98.04 mg Cd per g biomass.     

市政污泥热解产油影响因素及产物应用特性

利用外热式固定床反应器,研究终温、反应时间、升温速率等因素对市政污泥热解产油率的影响,并对产物特性进行了讨论。结果表明,热解终温及反应时间显著影响焦油产率,500 ℃是适宜的污泥热解温度,焦油产率达24.74%,温度继续升高则半焦缩聚反应强烈,热解气产率大幅增加,焦油产率基本恒定;在10 ℃·min-1的升温速率条件下,热解终温500 ℃,维持20 min,焦油产率可达到平衡;升温速率对焦油产率的影响不显著,热解反应达到平衡时,不同升温速率条件下,焦油产率相似;污泥焦油组分与中低温煤焦油相近,具备提酚、制燃料油和特种油品的潜力;污泥半焦灰分高,固定碳含量低,具有一定热值,比表面积较发达,掺混燃烧、制备吸附剂是其重要的潜在利用方向。     

The conversion of chicken manure to biooil by fast pyrolysis II. Analysis of chicken manure,biooils, and char by curie-point pyrolysis-gas chromatography/mass spectrometry (Cp Py-GC/MS)

The initial chicken manure and the three fractions derived from it by fast pyrolysis, that is, the two biooils Fractions I and II as well as the residual char were analyzed by Curie-point pyrolysis-gas chromatography/mass spectrometry (Cp Py-GC/MS). The individual compounds identified were grouped into the following six compound classes: (a) N-heterocyclics; (b) substituted furans; (c) phenol and substituted phenols; (d) benzene and substituted benzenes; (e) carbocyclics; and (f) aliphatics. Of special interest were the relatively high concentrations of N-heterocyclics in biooil Fraction II which was obtained in the highest yield and had the highest calorific value. Prominent N-heterocyclics in biooil Fraction II were methyl-and ethyl-substituted pyrroles, pyridines, pyrimidine, pyrazines, and pteridine. Also noteworthy was the high abundance of aliphatics in biooil Fraction I and the char. The alkanes and alkenes in biooil Fraction I ranged from n-C₇ to n-C₁₈ and C_7:1 to C_18:1, respectively, and those in the char from n-C₇ to n-C₁₉ and C_7:1 to C_19:1, respectively. The N-heterocyclics in the two biooil Fractions came from the chicken manure, from proteinaceous materials during fast pyrolysis or were formed during the fast pyrolysis manure conversion by the Maillard reaction which involved the formation of N-heterocyclics by amino acids interacting with sugars.     

The conversion of chicken manure to biooil by fast pyrolysis II. Analysis of chicken manure, biooils, and char by curie-point pyrolysis-gas chromatography/mass spectrometry (Cp Py-GC/MS)

The initial chicken manure and the three fractions derived from it by fast pyrolysis, that is, the two biooils Fractions I and II as well as the residual char were analyzed by Curie-point pyrolysis-gas chromatography/mass spectrometry (Cp Py-GC/MS). The individual compounds identified were grouped into the following six compound classes: (a) N-heterocyclics; (b) substituted furans; (c) phenol and substituted phenols; (d) benzene and substituted benzenes; (e) carbocyclics; and (f) aliphatics. Of special interest were the relatively high concentrations of N-heterocyclics in biooil Fraction II which was obtained in the highest yield and had the highest calorific value. Prominent N-heterocyclics in biooil Fraction II were methyl-and ethyl-substituted pyrroles, pyridines, pyrimidine, pyrazines, and pteridine. Also noteworthy was the high abundance of aliphatics in biooil Fraction I and the char. The alkanes and alkenes in biooil Fraction I ranged from n-C7 to n-C18 and C7:1 to C18:1, respectively, and those in the char from n-C7 to n-C19 and C7:1 to C19:1, respectively. The N-heterocyclics in the two biooil Fractions came from the chicken manure, from proteinaceous materials during fast pyrolysis or were formed during the fast pyrolysis manure conversion by the Maillard reaction which involved the formation of N-heterocyclics by amino acids interacting with sugars.     

Biotoxicity of nickel oxide nanoparticles and bio-remediation by microalgae Chlorella vulgaris

Adverse effects of manufactured nickel oxide nanoparticles on the microalgae Chlorellavulgaris were determined by algal growth-inhibition test and morphological observation via transmission electron microscopy (TEM). Results showed that the NiO nanoparticles had severe impacts on the algae, with 72 h EC(50) values of 32.28 mg NiOL(-1). Under the stress of NiO nanoparticles, C. vulgaris cells showed plasmolysis, cytomembrane breakage and thylakoids disorder. NiO nanoparticles aggregated and deposited in algal culture media. The presence of algal cells accelerated aggregation of nanoparticles. Moreover, about 0.14% ionic Ni was released when NiO NPs were added into seawater. The attachment of aggregates to algal cell surface and the presence of released ionic Ni were likely responsible for the toxic effects. Interestingly, some NiO nanoparticles were reduced to zero valence nickel as determined by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analysis. The maximum ratios of nickel reduction was achieved at 72 h of exposure, in accordance with the time-course of changes in soluble protein content of treated C. vulgaris, implying that some proteins of algae are involved in the process. Our results indicate that the toxicity and bioavailability of NiO nanoparticles to marine algae are reduced by aggregation and reduction of NiO. Thus, marine algae have the potential for usage in nano-pollution bio-remediation in aquatic system.     

Research progress and hot spots of hydrothermal liquefaction for bio-oil production based on bibliometric analysis

Environmental Science and Pollution Research - Hydrothermal liquefaction (HTL) of biomass used HTL reaction under high temperature and pressure to produce bio-oil. This technology is considered as...     

气相色谱/质谱测定苯酚丙酮生产废水中半挥发性有机物

建立了用二氯甲烷液液萃取对苯酚丙酮生产废水进行预处理,气相色谱/质谱法同时测定废水中半挥发性有毒有机物异丁酸、异丙苯、α-甲基苯乙烯、2-苯基丙醛、苯乙酮、2-苯基-2-丙醇、α-甲基苯甲醇、苯酚和苯甲酸等的定性定量分析方法。色谱条件为:DB-17MS型色谱柱,程序升温,进样量为1μL,质量选择检测器(MSD)。实验结果表明,该色谱条件对苯酚丙酮生产废水中各半挥发性组分具有较好的分离效果。而对9种组分的最低检出限均低于0.04mg/L,精密度实验相对标准偏差2.14%～5.15%,实际水样的加标回收率稳定。苯酚丙酮生产废水中的主要污染物为2-苯基-2-丙醇,其次为苯酚、异丁酸和异丙苯。     

The conversion of chicken manure to bio-oil by fast pyrolysis. III. Analyses of chicken manure, bio-oils and char by Py-FIMS and Py-FDMS

Fast pyrolysis of chicken manure produced the following three fractions: bio-oil Fraction I, bio-oil Fraction II, and a char. In a previous investigation we analyzed each of the four materials by curie-point pyrolysis-gas chromatography/mass spectrometry (CpPy-FDMS). The objective of this article is to report on the analyses of the same chicken manure and the three fractions derived from it by fast pyrolysis. We now used pyrolysis-field ionization mass spectrometry (Py-FIMS) to characterize the three fractions. In addition, the two bio-oil materials were analyzed by pyrolysis-field desorption mass spectrometry (Py-FDMS). The use of both Py-FIMS and Py-FDMS produced signals over significantly wider mass ranges than did CpPy-GC/MS, and so allowed us to identify considerably larger numbers of constituents in each material. Individual compounds identified in the mass spectra were classified into the following twelve compound classes: (a) low molecular weight compounds (< m/z 62); (b) carbohydrates; (c) phenols + lignin monomers; (d) lignin dimers; (e) n-alkylbenzenes; (f) N-heterocyclics; (g) n-fatty acids; (h) n-alkanes; (i) alkenes; (j) sterols; (k) n-diols and (l) high molecular weight compounds (> m/z 562). Of special interest were the high abundances of low-molecular weight compounds in the two bio-oils which constituted close to one half of the two bio-oils. Prominent among these compounds were water, ammonia, acetic acid, acetamide, propyl radical, formamide and hydrogen cyanide. The main quantitative differences between the two bio-oils was that bio-oil Fraction I, as analyzed by the two mass spectrometric methods, contained lower concentrations of low-molecular weight compounds, carbohydrates, and N-heterocyclics than bio-oil Fraction II but was richer in lignin dimers, n-alkylbenzenes and aliphatics (n-fatty acids, n-alkanes, alkenes, and n-diols). Of special interest were the N-heterocyclics in the two bio-oils such as pyrazole, pyrazoline, substituted pyrroles, pyridine and substituted pyridines, substituted methoxazole, substituted pyrazines, indole and substituted indoles. Fatty acids in all four materials ranged from n-C(9) to n-C(33), alkanes from n-C(9) to n-C(40), alkenes from C(10:1) to C(40:1) and diols from n-C(7) to n-C(29). The chicken manure, bio-oil Fraction I, and char each contained about 4% sterols with cholesterol, ethylcholestriene, ergosterol, ethylcholestene, ethylcholesterol and beta -sitosterol as major components. Semi-quantitative estimates of the total materials identified by Py-FIMS were: chicken manure: 61.1%; bio-oil Fraction I: 81.3%; bio-oil Fraction II: 78.6%; char: 61.3%; and by Py-FDMS were: bio-oil Fraction I: 65.4%; bio-oil Fraction II: 70.0%.     

Determination of acidic herbicides in cereals by QuEChERS extraction and LC/MS/MS

A simple and rapid method has been studied for the determination of acidic herbicides (2,4-D, Dichlorprop, Dichlorprop-p, Fluazifop, Fluroxypyr, MCPA, Mecoprop and Mecoprop-p) on cereals (rye). The method involves an alkaline hydrolysis with sodium hydroxide in order to release covalently bound compounds, prior to QuEChERS extraction, followed by neutralization and analysis via liquid chromatography-double mass spectrometry LC/MS/MS. The performance of the method either with or without alkaline hydrolysis was studied in terms of recovery rates and limit of quantification (LOQ). In either case, recoveries were determined at four spiking levels (0.02 mg/kg, 0.05 mg/kg, 0.1 mg/kg and 0.5 mg/kg) with 5 replicates for each level. Mean recoveries ranged from 90 to 120 %, whereas relative standard deviations (RSD %) proved to be less than 20 %. Quantitative analysis was carried out by the internal standard (Nicarbazin) and the LC/MS/MS analysis was performed in electrospray ionisation (ESI) negative mode using a Zorbax XCB Eclipse column. The developed method was applied to the analysis of several cereals commercially available like as rye flour, oat meal, oat flakes and dehusked oat. Residue levels were found below the limit of quantification (LOQ) of the method. The method has been tested in EU Proficiency Tests for cereals with good results.     

Isomeric analysis of PCDD/PCDF in waste incinerator fly ash by GC-MS/MS

The development of an analytical method for the analysis of PCDD/PCDF in flyash using a bench analytical system comprising of a gas chromatograph fitted with an ion trap detector operated in the tandem MS mode is described. The optimum settings for the most important MS/MS parameters are given, including those for the less reported mono- to tri-chlorinated dioxin and furan congener groups. Flyash samples from three waste incineration plants representing a decommissioned 1970s plant design, an upgraded and still operating plant originally designed in the 1970s, and a modern 1990s design operating plant have been analysed for PCDD/PCDF. The flyash samples were analysed for PCDD/PCDF using the methods developed and the total PCDD/PCDF, I-TEQ values and isomeric profiles are reported. The flyash from the older decommissioned incinerator had very significantly higher concentrations of PCDD/PCDF compared to the modern incinerator flyash.     

Analysis of dioxins and furans in environmental samples by GC-ion-trap MS/MS

The work aims to characterise PCDDs/Fs in environmental matrices by high resolution gas chromatography coupled to low resolution quadrupole ion-trap mass spectrometry (GC-QITMS/MS). In particular, the study was mainly focused in different environmental samples such as sewage sludge, soils, and sediments and in combustion residues as fly ashes. Previous experiences have already detected and quantified PCDDs/PCDFs in all matrices studied. Moreover, isomer-specific analysis of 2,3,7,8-PCDDs/Fs compounds corroborated good correlation between GC-QITMS/MS and a well-established technique such as high resolution mass spectrometry (HRMS). Finally, QC measures included the participation in intercalibration exercises. Successful results were achieved using GC-QITMS/MS in the analysis of fly ashes, soils and sediment materials. In general, GC-QITMS/MS constitutes an interesting alternative for routine analysis of dioxins in such as matrices.     

Analysis of chlorothalonil and degradation products in soil and water by GC/MS and LC/MS

We present a method using gas chromatography (GC) and liquid chromatography (LC) coupled to a mass selective detector to measure concentrations of the fungicide chlorothalonil and several of its metabolites in soil and water. The methods employed solid-phase extraction using a hydrophobic polymeric phase for the isolation of analytes. In lake water, average analyte recoveries ranged from 70% to 110%, with exception of pentachloronitrobenzene that gave low recoveries (23%). The method detection limits were determined to be in the range of 1 and 0.1microg l(-1) for the LC and GC methods, respectively. In soil samples, recoveries ranged from 80% to 95% for 4-hydroxy-2,5,6-trichloroisophthalonitrile (metabolite II) and 1,3-dicarbamoyl-2,4,5,6-tetrachlorobenzene (metabolite III). Limits of detection (LOD) were 0.05 and 0.02microg g(-1), respectively. Chlorothalonil and other metabolites were analyzed by GC giving recoveries ranging from 54% to 130% with LOD of 0.001-0.005microg g(-1).     

Population growth of Euchlanis dilatata (Rotifera): combined effects of methyl parathion and food (Chlorella vulgaris)

In the present work, the combined impact of four concentrations (0, 0.0625, 0.125, and 0.25 mg/L) of methyl parathion and three densities (0.5 x 10(6), 1.0 x 10(6), and 2.0 x 10(6) cells/mL) of the green alga Chlorella vulgaris on the population growth of Euchlanis dilatata was studied. In general, regardless of the food level, an increase in the concentration of methyl parathion resulted in a significant reduction of the maximal population density and rate of population increase. The population growth rate in the controls ranged from 0.248 to 0.298; rates were lower in the presence of the pesticide. At any toxicant concentration, rotifers fed higher algal density showed significantly higher population growth compared with those at lower food levels. An interaction between toxicant and food level was evident on the population growth of E. dilatata. Results have been discussed in light of the protective role of algal density on the toxic effects of insecticides on rotifers and the differences in susceptibility to toxicants between planktonic and littoral rotifers.     

芦苇秸秆厌氧发酵影响因素正交实验及产气潜力研究

以芦苇秸秆为发酵原料,采用正交实验法,在湿式和干式批次发酵条件下,考察了预处理方式、发酵浓度和接种量对芦苇厌氧发酵沼气产量的影响。结果表明,以NaOH预处理、接种量30%、TS浓度12 %的处理发酵情况最好,在第3 天即出现产气高峰,最高日产气量达2.1 L,总产气量达42.8 L。芦苇的总TS和总VS产气率分别达285.7 L·kg-1 TS、402.8 L·kg-1 VS,具有较高的产气潜力。根据正交实验方差分析结果,芦苇厌氧发酵的影响因素的影响程度是预处理方式 > 发酵浓度 > 接种量,确定芦苇厌氧发酵的最佳工艺条件为：NaOH预处理、接种量100 %、发酵浓度TS 12 %。     

Biodegradation of juvenoid diastereoisomers: radio-HPLC and MS analysis

Microbial degradation of two diastereoisomeric forms 2 and 3 of a selected juvenoid (insect juvenile hormone bioanalog), ethyl N-{2-{4-[(2-hydroxycyclohexyl)methyl]phenoxy}ethyl}carbamate was studied and the degradation products analyzed. Degradation experiments were performed using simple modeling under laboratory conditions. A Candida sp. strain T1, isolated from soil, was chosen as a biodegradation species. Radiolabeling of the studied compounds 2 and 3 was used in combination with radio-HPLC and MS analysis to increase the limits of detection, monitoring and isolation of trace quantities of the products of degradation and/or transformation. Resulting from the microbial processes using 2 or 3 as source compounds, three identical products (4-6) of their biodegradation were produced. Compound 2 also afforded two additional products (7, 8). Radio-HPLC analysis and separation, and subsequent MS analysis of the degradation mixtures resulted in identification of the degradation products. The degree and the rate of biodegradation of 2 and 3 were analyzed after 1, 3 and 7 days from the beginning of the experiment.     

Degradation dynamics,residues and risk assessment of Dufulin enantiomers in corn plants and corn by LC/MS/MS

ABSTRACT

The degradation dynamics and terminal residues of dufulin enantiomers were investigated in two typical corn plants. A convenient and precise chiral method by high-performance liquid chromatography coupled with tandem triple quadrupole mass spectrometry (HPLC/MS/MS) using a Chiralpak IC column was developed and validated for measuring dufulin enantiomers in corn plants and corn. The two enantiomers of dufulin quickly dissipated in the corn plant, and no noticeable stereoselectivity was observed during degradation or in the final residues. After 30% rac-dufulin wettable powder with a 1- to 1.5-fold dose of the recommended value was sprayed two to three times on corn plants, the residue levels of S-(+)-dufulin and R-(-)-dufulin in corn from both sites were lower than or equal to 0.0520 mg kg^–1 on days 7, 14 and 21 after the last application. The dietary risk assessment indicated that dufulin did not exhibit obvious dietary health risks in corn samples when good agricultural practices were implemented. The findings from this study may be used to better understand the chiral profiles of dufulin in the environment and the effect of dufulin residues in corn on health.     

PAHs analysis of fish whole gall bladders and livers from the Natural Reserve of Camargue by GC/MS

Traces of parent polycyclic aromatic hydrocarbons (PAH) in fish whole gall bladders and livers from the Natural Reserve of Camargue were determined from three different species: cels, goldfishes and catfishes by capillary gas chromatography-mass spectrometry (GC/MS) after Soxhlet extraction and florisil column cleanup. Results have been successfully correlated with biological fish parameters in order to identify adequate biomarkers of PAHs contamination.     

Characterisation of odorants emissions from landfills by SPME and GC/MS

Odorous compounds from a landfill have been characterised by gas-chromatography-mass-spectrometry, identifying about 100 volatile organic compounds. Air samples from different landfill sites and from the environment have been analysed after a solid-phase microextraction on a three-phase fiber, DVB/Carboxen/PDMS, which allowed a preconcentration and the chromatographic data obtained from the most significant emission sources have been submitted to chemometric analysis in order to better establish specific markers of olfactory pollution. For example limonene was a typical tracer of fresh wastes, while p-cymene was characteristic of leachate and biogas. By the developed analytical procedure it has been evaluated the efficiency of a scrubber plant utilised in the landfill in order to remove malodour compounds. The average removal efficiency was not very high (about 23.5%) due to scarce ability in removing low polarity compounds. Furthermore, it has been demonstrated the suitability of a microgas chromatograph for the continuous on-site monitoring of air pollution in order to rapidly individuate emission sources of olfactive nuisances.     

Development of in-house ELISA for detection of chloramphenicol in bovine milk with subsequent confirmatory analysis by LC-MS/MS

This study was undertaken to develop and validate direct competitive ELISA for the determination of chloramphenicol residues in bovine milk. Antisera and an enzyme-tracer for chloramphenicol were prepared and used to develop an ELISA with inhibition concentrations, IC₂₀ and IC₅₀, of 0.09 and 0.44 ng mL^?1, respectively. Milk samples were spiked with standards equivalent to 0, 0.2, 0.3, 0.5, 1.0 &; 1.5 ng mL^?1 and extracted in methanol. The mean recoveries were found to be 73–100% with coefficient of variance 7–11%. The decision limit (CCα) and detection capability (CCβ) were calculated as 0.10 and 0.12 ng mL^?1, respectively. The results were found comparable with the commercial ELISA, having recoveries of 87 to 100%, CCα 0.09 ng mL^?1 and CCβ 0.12 ng mL^?1. As per Commission Decision 2002/657/EC, in-house ELISA was further validated by using LC-MS/MS. Mass spectral acquisition was done by using electrospray ionization in the negative ion mode applying single reaction monitoring of the diagnostic transition reaction for CAP (m/z 152, 194 and 257). The calibration curve showed good linearity in concentrations from 0.025 to 1.6 ng mL^?1 with correction coefficient 0.9902. The mean recoveries were found to be 88 to 100%. The CCα was calculated as 0.057 ng mL^?1 and CCβ 0.10 ng mL^?1. Since CCα and CCβ are less than half of the MRPL (0.15 ng mL^?1), the test was found suitable for screening and quantification of CAP residues in bovine milk samples. Results of surveillance studies indicated that out of 31 analyzed milk samples, 12.9% samples were found with CAP residues but only 3.2% samples were declared positive with maximum concentration 0.31 ng mL^?1, slightly above the MRPL.     

The endocrine disrupting potential of sediments from the Upper Danube River (Germany) as revealed by in vitro bioassays and chemical analysis

Introduction  

The present study was part of a comprehensive weight-of-evidence approach with the goal of identifying potential causes for the declines in fish populations, which have been observed during the past decades in the Upper Danube River.