Variability in the content and composition of alkaloid found in Canadian ergot. iii. triticale and barley∗

Abstract

The total alkaloid content and individual alkaloid composition were determined by colorimetry and high performance liquid chromatography, respectively, for Canadian triticale and barley ergot (Claviceps purpurea). The total alkaloid content was highly variable between individual sclerotia from the same or different sources and ranged from 0.042 to 0.752% for triticale and from 0.082 to 1.04% for barley; average values were 0.239% for Ottawa triticale, 0.289% for Prairie triticale, and 0.264% for barley. Ergocristine and its isomer ergocristinine were the major constituents in both grains. On average, Canadian ergot pooled from rye, wheat, triticale, and barley consists of ergocristine (31%), ergocristinine (13%), ergocristinine (13%), ergotamine (17%), ergotaminine (8%), ergocryptine (5%), ergocryptinine (3%), ergo‐metrine (5%), ergometrinine (2%), ergosine (4%), ergosinine (2%), ergocornine (4%), ergocorninine (2%), and unidentified alkaloids (3%) and an average total alkaloid content of 0.236%. With the exception of rye and barley ergot from the maritime regions, Canadian rye, wheat, triticale, and barley ergot is fairly uniform in individual alkaloid composition.     

Simultaneous determination of pesticides,mycotoxins, tropane alkaloids,growth regulators,and pyrrolizidine alkaloids in oats and whole wheat grains after online clean-up via two-dimensional liquid chromatography tandem mass spectrometry

In this study, a two-dimensional liquid chromatography tandem mass spectrometry method was developed and validated for the determination of pesticide residues and contaminants in whole wheat grains and oats. The samples were extracted with a mixture of acetonitrile and water and were injected into the two-dimensional LC-MS/MS system without any further clean-up or sample preparation. Samples were analyzed with four different matrix matched calibrations. Matrix effects were evaluated by comparing analyte signals in the respective matrix matched standard with the neat solvent standards. The final method was validated according to the current Eurachem validation guide and SANTE document. The number of successfully validated analytes throughout all three validation levels in oats and wheat, respectively, were as follows: 330 and 316 out of 370 pesticides, 6 and 13 out of 18 pyrrolizidine alkaloids and 7 out of 9 regulated mycotoxins. Moreover, both plant growth regulators mepiquat and chlormequat as well as the tropane alkaloids atropine and scopolamine met the validation criteria. The majority of pesticides showed limits of detection below 1?µg kg^?1, pyrrolizidine alkaloids below 0.7?µg kg^?1, tropane alkaloids below 0.2?µg kg^?1, growth regulators below 0.7?µg kg^?1 and mycotoxins below 8?µg kg^?1 in both matrices.     

北京市场水性建筑涂料VOCs成分及含量分析

为获取北京地区水性建筑涂料挥发性有机物含量和成分谱,从北京市4个较大的建材市场取用水性建筑内外墙涂料各20种,共计40个样品进行测试分析。样品预处理采用超声波萃取法,以乙腈为萃取剂,通过正交实验确定了VOCs样品预处理的中硫酸钠使用量、超声波萃取时间和离心机转速的最佳条件。以22种VOCs作为标准物质使用GC-FID对样品进行测试,采用外标法定量,获得了水性建筑内外墙涂料的VOCs含量以及组分分布特征。结果显示,水性内墙涂料VOCs含量为282.85~12 814.40 mg·kg-1,乙二醇和1,2丙二醇为主要VOCs组分,含量分别为174.39~11 395.47 mg·kg-1和759.08~6 283.77 mg·kg-1,占比分别为2.60%~96.73%和10.96%~90.79%。水性外墙涂料含量为766.11~73 479.74 mg·kg-1,乙二醇、乙二醇单丁醚、二乙二醇等含量较高,含量分别为255.28~14 172.62、503.31~16 039.12和37.81~32 291.22 mg·kg-1,占比分别为4.53%~98.49%、1.3%~61.98%和0.24%~45.90%。     

A high pressure liquid chromatographic method for the analysis of zearalenone in chicken blood

Abstract

A high pressure liquid chromatographic (HPLC) method is described to determine zearalenone in chicken blood. Samples are extracted with acetonitrile, followed by a hexane cleanup procedure and extracted further with ethyl acetate. The analysis of zearalenone is by HPLC using a reverse phase radial compression separation system, an ultraviolet absorbance detector and a mobile phase of acetonitrile‐water 60:40 (v/v). Recoveries of zearalenone in blood at levels of 50–200 ng/ml are in the range of 66.8–72.6%.     

Sub-tropical urban environment affecting content and composition of non-structural carbohydrates of Lolium multiflorum ssp. italicum cv. Lema

This study analyzed the relationship between environmental factors, especially air pollution and climatic conditions, and non-structural carbohydrates (NSC) in plants of Lolium multiflorum exposed during 10 consecutive periods of 28 days at a polluted site (Congonhas) and at a reference site in São Paulo city (Brazil). After exposure, NSC composition and leaf concentrations of Al, Fe, Cu, Zn, Pb and Cd were measured. The seasonal pattern of NSC accumulation was quite similar in both sites, but plants at Congonhas showed higher concentrations of these compounds, especially fructans of low and medium degree of polymerization. Regression analysis showed that NSC in plants growing at the polluted site were explained by variations on temperature and leaf concentration of Fe (positive effect), as well as relative humidity and particulate material (negative effect). NSC in the standardized grass culture, in addition to heavy metal accumulation, may indicate stressing conditions in a sub-tropical polluted environment.     

Simultaneous Determination of Imidacloprid,Thiacloprid, and Thiamethoxam in Soil and Water by High-performance Liquid Chromatography with Diode-array Detection

Abstract

A high-performance liquid chromatography method with diode-array detection (HPLC-DAD) is described for the determination of three neonicotinoid insecticides imidacloprid, thiacloprid, and thiamethoxam in soil and water. The soil samples were extracted with acetonitrile, while the water samples were extracted using C₁₈ cartridges. The mean recoveries plus standard deviations for spiked soil samples were 82 ± 4.2% for thiamethoxam, 99 ± 4.2% for imidacloprid and 94 ± 1.4% for thiacloprid. The recoveries for water samples ranged from 87 ± 3.4% for thiamethoxam to 97 ± 3.9% for imidacloprid and 97 ± 2.6% for thiacloprid. The limits of quantitation (LOQ) were 0.1, 0.1, 0.01 mg/kg in soil (5 g), and 2, 2, 0.5 µg/L in water (50 mL) for thiamethoxam, imidacloprid, and thiacloprid, respectively.     

Seasonal variations in the chemical composition of particulate matter: a case study in the Po Valley. Part I: macro-components and mass closure

The seasonal variability in the mass concentration and chemical composition of atmospheric particulate matter (PM₁₀ and PM_2.5) was studied during a 2-year field study carried out between 2010 and 2012. The site of the study was the area of Ferrara (Po Valley, Northern Italy), which is characterized by frequent episodes of very stable atmospheric conditions in winter. Chemical analyses carried out during the study allowed the determination of the main components of atmospheric PM (macro-elements, ions, elemental carbon, organic matter) and a satisfactory mass closure was obtained. Accordingly, chemical components could be grouped into the main macro-sources of PM: soil, sea spray, inorganic compounds from secondary reactions, vehicular emission, organics from domestic heating, organics from secondary formation, and other sources. The more significant seasonal variations were observed for secondary inorganic species in the fine fraction of PM; these species were very sensitive to air mass age and thus to the frequency of stable atmospheric conditions. During the winter ammonium nitrate, the single species with the highest concentration, reached concentrations as high as 30 μg/m³. The intensity of natural sources was fairly constant during the year; increases in natural aerosols were linked to medium and long-range transport episodes. The ratio of winter to summer concentrations was roughly 2 for combustion product, close to 3 for secondary inorganic species, and between 2 and 3 for organics. The winter increase of organics was due to poorer atmospheric dispersion and to the addition of the emission from domestic heating. A similar winter to summer ratio (around 3) was observed for the fine fraction of PM.     

Composition and effects of inhalable size fractions of atmospheric aerosols in the polluted atmosphere: Part I. PAHs,PCBs and OCPs and the matrix chemical composition

Atmospheric particulate matter (PM) abundance, mass size distribution (MSD) and chemical composition are parameters relevant for human health effects. The MSD and phase state of semivolatile organic pollutants were determined at various polluted sites in addition to the PM composition and MSD. The distribution pattern of pollutants varied from side to side in correspondence to main particle sources and PM composition. Levels of particle-associated polycyclic aromatic hydrocarbons (PAHs) were 1–30 ng m^?3 (corresponding to 15–35 % of the total, i.e., gas and particulate phase concentrations), of polychlorinated biphenyls (PCBs) were 2–11 pg m^?3 (4–26 % of the total) and of DDT compounds were 2–12 pg m^?3 (4–23 % of the total). The PM associated amounts of other organochlorine pesticides were too low for quantification. The organics were preferentially found associated with particles <0.45 μm of aerodynamic equivalent diameter. The mass fractions associated with sub-micrometer particles (PM_0.95) were 73–90 %, 34–71 % and 36–81 % for PAHs, PCBs and DDT compounds, respectively. The finest particles fraction had the highest aerosol surface concentration (6.3–29.7)_×10^?6 cm^?1 (44–70 % of the surface concentration of all size fractions). The data set was used to test gas-particle partitioning models for semivolatile organics for the first time in terms of the organics' MSD and size-dependent PM composition. The results of this study prove that at the various sites particles with diverse size, matrix composition, amount of contaminants and toxicological effects occur. Legislative regulation based on gravimetric determination of PM mass can clearly be insufficient for assessment.     

不同温度水热处理对高含固污泥有机物转化及组分的影响

以城市污水处理厂的高含固污泥为研究对象,探讨其在不同水热预处理温度条件下,污泥中有机物水解效果及组分构成的变化情况。结果表明：在不同的水热预处理温度下(140、170、200、230和260 ℃),均可有效地水解污泥中有机物;在温度170 ℃的条件下预处理30 min,水解后的污泥中,SCOD、溶解性蛋白质和溶解性碳水化合物浓度均达到最高,分别为40.71、20.56和9.10 g·L⁻¹。对水解上清液进行傅里叶红外分析发现,在170 ℃时,污泥中的蛋白质和碳水化合物被充分水解,上清液中含有大量O—H键。对水解上清液进行三维荧光检测结合积分区域法(FRI)分析发现,在170 ℃时,可生物利用的微生物代谢产物所占比例最大(38.68%),微生物难降解的腐殖酸类物质所占比例最小(37.47%)。高含固污泥在170 ℃、30 min的预处理条件下,污泥中大分子有机物被分解为小分子有机物;同时,可供微生物利用物质所占比例最大,更有利于污泥后续的资源化利用。     

Acid generation upon thermal concentration of natural water: The critical water content and the effects of ionic composition

Thermal evaporation of a variety of simulated pore waters from the region of Yucca Mountain, Nevada, produced acidic liquids and gases during the final stages of evaporation. Several simulated pore waters were prepared and then thermally distilled in order to collect and analyze fractions of the evolved vapor. In some cases, distillates collected towards the end of the distillation were highly acidic; in other cases the pH of the distillate remained comparatively unchanged during the course of the distillation. The results suggest that the pH values of the later fractions are determined by the initial composition of the water. Acid production stems from the hydrolysis of magnesium ions, especially at near dryness. Near the end of the distillation, magnesium nitrate and magnesium chloride begin to lose water of hydration, greatly accelerating their thermal decomposition to form acid. Acid formation is promoted further when precipitated calcium carbonate is removed. Specifically, calcium chloride-rich pore waters containing moderate (10–20 ppm) levels of magnesium and nitrate and low levels of bicarbonate produced mixtures of nitric and hydrochloric acid, resulting in a precipitous drop in pH to values of 1 or lower after about 95% of the original volume was distilled. Waters with either low or moderate magnesium content coupled with high levels of bicarbonate produced slightly basic fractions (pH 7–9). If calcium was present in excess of bicarbonate, waters containing moderate levels of magnesium produced acid even in the presence of bicarbonate, due to the precipitation of calcium carbonate. Other salts such as halite and anhydrite promote the segregation of acidic vapors from residual basic solids. The concomitant release of wet acid gas has implications for the integrity of the alloys under consideration for containers at the Yucca Mountain nuclear waste repository. Condensed acid gases at very low pH, especially mixtures of nitric and hydrochloric acid, are capable of corroding even alloys, such as nickel-based Alloy 22, which are considered to be corrosion-resistant under milder conditions.     

Aerosol composition as a function of haze and humidity levels in the Southwestern U.S.

The observed composition of visibility-reducing aerosols in the Grand Canyon region is summarized in climatological terms. Observations are from SCENES, a measurement program extending from 1984 to 1989. Results are presented as average mass balances stratified by various factors.Aerosols were found to exhibit substantial seasonal variation, but little systematic diurnal variation. Crustal material was a dynamic component, and peaked during springtime. Aerosol composition, but not total concentration, depended strongly on ambient relative humidity, with crustal material augmented at low humidities and sulfates augmented at high humidities. Total fine-particle concentrations correlated strongly with light scattering, as expected; however, little association between chemical composition and light scattering was observed.     

Climate Variability and Environmental Stress in the Sudan-Sahel Zone of West Africa

Environmental change in the Sudan-Sahel region of West Africa (SSWA) has been much debated since the droughts of the 1970s. In this article we assess climate variability and environmental stress in the region. Households in Senegal, Mali, Burkina Faso, Niger, and Nigeria were asked about climatic changes and their perceptions were compared across north–south and west–east rainfall gradients. More than 80% of all households found that rainfall had decreased, especially in the wettest areas. Increases in wind speeds and temperature were perceived by an overall 60–80% of households. Contrary to household perceptions, observed rainfall patterns showed an increasing trend over the past 20 years. However, August rainfall declined, and could therefore potentially explain the contrasting negative household perceptions of rainfall trends. Most households reported degradation of soils, water resources, vegetation, and fauna, but more so in the 500–900 mm zones. Adaptation measures to counter environmental degradation included use of manure, reforestation, soil and water conservation, and protection of fauna and vegetation. The results raise concerns for future environmental management in the region, especially in the 500–900 mm zones and the western part of SSWA.     

Pharmaceuticals and personal care products found in the Great Lakes above concentrations of environmental concern

The monitoring of pharmaceuticals and personal care products (PPCPs) has focused on the distribution in rivers and small lakes, but data regarding their occurrence and effects in large lake systems, such as the Great Lakes, are sparse. Wastewater treatment processes have not been optimized to remove influent PPCPs and are a major source of PPCPs in the environment. Furthermore, PPCPs are not currently regulated in wastewater effluent. In this experiment we evaluated the concentration, and corresponding risk, of PPCPs from a wastewater effluent source at varying distances in Lake Michigan. Fifty-four PPCPs and hormones were assessed on six different dates over a two-year period from surface water and sediment samples up to 3.2 km from a wastewater treatment plant and at two sites within a harbor. Thirty-two PPCPs were detected in Lake Michigan and 30 were detected in the sediment, with numerous PPCPs being detected up to 3.2 km away from the shoreline. The most frequently detected PPCPs in Lake Michigan were metformin, caffeine, sulfamethoxazole, and triclosan. To determine the ecological risk, the maximum measured environmental concentrations were compared to the predicted no-effect concentration and 14 PPCPs were found to be of medium or high ecological risk. The environmental risk of PPCPs in large lake systems, such as the Great Lakes, has been questioned due to high dilution; however, the concentrations found in this study, and their corresponding risk quotient, indicate a significant threat by PPCPs to the health of the Great Lakes, particularly near shore organisms.     

Oil residues in Baltic sediment,mussel and fish. I. Development of the analysis methods

Sediment, sediment trap, Mytilus, Macoma and flounder samples from Northern Baltic (Finnish archipelago) have been analyzed for their contents of aliphatic and aromatic hydrocarbons. Androstane and hexaethylbenzene were used as internal standards. The analysis procedure consisted of alkaline degradation of fat, column fractionation of the two residue groups and final determination by glass capillary gas chromatography with FID for aliphatic hydrocarbon group and with mass spectrometry for non-polar aromatic residue group. The latter group was also determined by high pressure liquid chromatography. The residues due to oil pollution were distinguished from compounds of pure natural origin on the basis of statistical treatment of the determination results.     

Humic acids from oxidized coals I. Elemental composition, titration curves, heavy metals in HA samples, nuclear magnetic resonance spectra of HAs and infrared spectroscopy

The formation of humic acids (HAs) from bituminous coal was verified by laboratory oxidation. In a relatively short time the oxidation by air at temperature above 150 degrees C led to the formation of HAs. These HAs were compared with those isolated from oxidized bituminous coal from the vicinity of red bed bodies, from weathered bituminous coal, oxihumolite and lignite. For this the organic and inorganic elemental composition of HAs, apparent dissociation constants, metal-binding capacities, nuclear magnetic resonance and infrared spectra were determined and evaluated. With increasing temperature of laboratory oxidation of bituminous coal the percentage of aromaticity of HAs increases. HAs prepared from coal oxidized at 150 degrees C are characterized by an aromaticity index 78% while for HAs prepared at 250 and 300 degrees C by 95% aromaticity. The same index for HAs isolated from naturally oxidized bituminous coals is of about 87% whereas it is of about 50% for oxihumolite and lignite. The apparent dissociation constants (Kapp) are much higher in HAs isolated from oxihumolite and lignite (pKapp from 3.35 to 3.80) than those from oxidized bituminous coal samples (pKapp from 4.47 to 4.85). There is a good negative correlation between Pb-binding capacity and pKapp of all samples suggesting that metallic ions are bonded to acidic groups of HAs. Also contents of inorganic elements like Fe, Al, Si are much higher in HAs isolated from lignite and oxihumolite than those in HAs from oxidized bituminous coal. Thus, it seems that the temperatures below 150 degrees C and the long oxidation time are necessary conditions for the formation of HAs in oxidative altered bituminous coal deposited deeply under the earth surface.     

Investigating the sources of the mutagenic activity found in a river using the Salmonella assay and different water extraction procedures

In the routine São Paulo state (Brazil) surface water quality-monitoring program, which includes the Salmonella microsome mutagenicity assay as one of its parameters, a river where water is taken and treated for drinking water purposes has repeatedly shown mutagenic activity. A textile dyeing facility employing azo-type dyes was the only identifiable source of mutagenic compounds. We extracted the river and drinking water samples with XAD4 at neutral and acidic pH and with blue rayon, which selectively adsorbs polycyclic compounds. We tested the industrial effluent, raw, and treated water and sediment samples with YG1041 and YG1042 and compared the results with the TA98 and TA100 strains. The elevated mutagenicity detected with YG-strains suggested that nitroaromatics and/or aromatic amines were causing the mutagenicity detected in the samples analyzed. Positive responses for the blue rayon extracts indicated that mutagenic polycyclic compounds were present in the water samples analyzed. The mutagen or mixture of mutagens present in the effluent and water samples cause mainly frameshift mutations and are positive with and without metabolic activation. The Salmonella assay combined with different extraction procedures proved to be very useful in the identification of the origin of the pollution and in the identification of the classes of chemical compounds causing the mutagenic activity in the river analyzed.     

The essential oil qualitative and quantitative composition in the needles of Pinus sylvestris L. growing along industrial transects

The aim of this study was to evaluate composition of the essential oils in the needles of Pinus sylvestris growing in the areas affected by a cement factory (CF), and an oil refinery (OR). Volatile components of the needles were analyzed by GC and GC/MS. The most heavily polluted CF stand had significantly higher concentration of gamma-Terpinene, Caryophyllene oxide in the current-year needles, while higher concentration of delta-3-Carene, alpha-Terpinene, gamma-Terpinene and Terpinolene was documented for 1-year-old needles. The most heavily polluted OR stand had a significantly higher concentration of Sabinene+beta-Pinene, 1-epi-Cubenol in the current-year needles and a significantly higher concentration of Camphene, Sabinene+beta-Pinene, Myrcene, alpha-Cadinene, 1-epi-Cubenol in the 1-year-old needles than the least polluted site. Along transects an increase in the amount of some diterpenes and a decrease in the components of the shorter chain essential oils was observed. These effects could be at least partially attributed to SO(2).     

Fate of cationic surfactants in the marine environment, I. Bioconcentration of long-chain alkylnitriles and trialkylamines

Long-chain alkylnitriles (C_nH_2n+1CN, where n=13, 15, 17) (LANs) and long-chain-trialkylamines (NC_mH_2m+1C_nH_2n+1C_jH_2j+1, where m,n = 1, 14, 16, 18 and j= 14, 16, 18) (TAMs) were identified for the first time in biota samples at concentrations ranging from 9–574 ng g⁻¹ and from 157 to 825 (fresh wt. basis), respectively. In addition, the simultaneous occurrence in the aquatic environment of LANs and TAMs were also reported for the first time. The Kb values of both, LANs and TAMs varyied according to the different species but their were comparable to those found for PAHs.     

Adaptation, validation and application of the chemo-thermal oxidation method to quantify black carbon in soils

The chemo-thermal oxidation method at 375 °C (CTO-375) has been widely used to quantify black carbon (BC) in sediments. In the present study, CTO-375 was tested and adapted for application to soil, accounting for some matrix specific properties like high organic carbon (≤39%) and carbonate (≤37%) content. Average recoveries of standard reference material SRM-2975 ranged from 25 to 86% for nine representative Swiss and Indian samples, which is similar to literature data for sediments. The adapted method was applied to selected samples of the Swiss soil monitoring network (NABO). BC content exhibited different patterns in three soil profiles while contribution of BC to TOC was found maximum below the topsoil at all three sites, however at different depths (60-130 cm). Six different NABO sites exhibited largely constant BC concentrations over the last 25 years, with short-term (6 months) prevailing over long-term (5 years) temporal fluctuations.