Analysis of phytochelatin complexes in the lead tolerant vetiver grass [Vetiveria zizanioides (L.)] using liquid chromatography and mass spectrometry

Ethylenediamene tetraacetic acid (EDTA) has been used to mobilize soil lead (Pb) and enhance plant uptake for phytoremediation. Chelant bound Pb is considered less toxic compared to free Pb ions and hence might induce less stress on plants. Characterization of possible Pb complexes with phytochelatins (PC_n, metal-binding peptides) and EDTA in plant tissues will enhance our understanding of Pb tolerance mechanisms. In a previous study, we showed that vetiver grass (Vetiveria zizanioides L.) can accumulate up to 19,800 and 3350 mg Pb kg⁻¹ dry weight in root and shoot tissues, respectively; in a hydroponics set-up. Following the basic incubation study, a greenhouse experiment was conducted to elucidate the efficiency of vetiver grass (with or without EDTA) in remediating Pb-contaminated soils from actual residential sites where Pb-based paints were used. The levels of total thiols, PC_n, and catalase (an antioxidant enzyme) were measured in vetiver root and shoot following chelant-assisted phytostabilization. In the presence of 15 mM kg ⁻¹ EDTA, vetiver accumulated 4460 and 480 mg Pb kg⁻¹ dry root and shoot tissue, respectively; that are 15- and 24-fold higher compared to those in untreated controls. Despite higher Pb concentrations in the plant tissues, the amount of total thiols and catalase activity in EDTA treated vetiver tissues was comparable to chelant unamended controls, indicating lowered Pb toxicity by chelation with EDTA. The identification of glutathione (referred as PC₁) (m/z 308.2), along with chelated complexes like Pb-EDTA (m/z 498.8) and PC₁-Pb-EDTA (m/z 805.3) in vetiver root tissue using electrospray tandem mass spectrometry (ES-MS) highlights the possible role of such species towards Pb tolerance in vetiver grass.     

Challenges to liberalism: The case of Australian energy policy

This paper considers liberal and nationalist economic policy approaches to the ownership and development of Australian energy resources (oil, gas, coal and uranium). In the two decades prior to 1983, Australia pursued economic policies in relation to its energy resources which could broadly be described as ‘nationalist’. Governments of the day intervened in development decisions in an effort to enhance the ‘national interest’. From 1983, along with the deregulation of the Australian economy as a whole, policy relating to energy resources was liberalised. Development of energy reserves henceforth occurred according to the dictates of the market. This paper argues that recent Australian energy policy initiatives reflect an increase in nationalist influences and a retreat from the liberalisation agenda that dominated energy policy making in the 1980s and 1990s. Three examples are discussed where policy has been influenced by a nationalist framework: (1) the domestic gas reservation policy in Western Australia; (2) Australian government efforts to promote a ‘value adding’ nuclear processing industry and (3) Australian Labor Party policy giving preferential financial incentives for gas to liquids projects. The re-emergence of nationalism in Australia is occurring either because policy makers now favour it as a path to energy security or in some cases because they believe that appeals to nationalism will generate political support.     

Screening analysis of volatile organic contaminants in commercial inorganic coagulants used for drinking water treatment

A method for quality screening is suggested to detect volatile impurities in inorganic coagulants that are used for drinking water treatment. Static headspace gas chromatography with mass spectrometry detection (HS–GCMS) is sensitive and selective to detect volatiles in low concentrations. This study has discovered that volatile organic impurities are detectable in ferric and aluminium-based coagulants which are used for drinking water treatment. For ferric chloride, 2-propanol was detected at a level of 17–24 μg ml⁻¹, acetone at 0.7–1.7 μg ml⁻¹, 1,1,1-trichloroacetone at 0.02–0.04 μg ml⁻¹, trichloromethane at 0.01–0.02 μg ml⁻¹ and toluene at 0.01–0.12 μg ml⁻¹. For ferric chloride sulfate, acetone was detected at a level of 0.12 μg ml⁻¹, 1,1,1-trichloroacetone at 0.06–0.08 μg ml⁻¹, trichloromethane at 0.13–0.23 μg ml⁻¹, bromodichloromethane at 0.04–0.06 μg ml⁻¹ and dibromochloromethane at 0.04–0.05 μg ml⁻¹. For aluminium hydroxide chloride, only trichloromethane was detectable, but below the method detection limits (MDL). Although the concentrations of these impurities in commercial coagulants are low, this observation is important and should have impact on water industries for them to pay attention to the chemicals they are using for drinking water production.     

Gas/particle partitioning of atmospheric PCDD/Fs in a satellite town in Eastern China

Gas/particle partitioning of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in ambient air was investigated in a satellite town in Eastern China from April 2007 to January 2008 comprehending large temperature variations (from 3 to 34 °C, daily average). Molecular weight, molecular structure and ambient temperatures are the three major factors that govern the gas/particle partitioning of atmospheric PCDD/Fs throughout the year. Generally, good agreements were obtained (except for winter) between measured particulate fractions and theoretical estimates of both the Junge–Pankow adsorption model and Harner Bidleman absorption model using different sets of subcooled liquid vapor pressure and octanol–air partition coefficient (K_oa), respectively. Models utilizing estimates, derived from gas chromatographic retention indices (GC-RIs), are more accurate than that of entropy-based. Moreover, during winter, the K_oa-based model using the GC-RIs approach performs better on lower chlorinated PCDD/Fs than that of -based. Furthermore, possible sources of mismatch between measured and predicted values in winter (3–7 °C) were discussed. Gas adsorption artifact was demonstrated to be of minor importance for the phenomena observed. On the other hand, large deviations of slopes (m_r) and intercepts (b_r) in logK_p vs. plots from theoretical values are observed in the literature data and these are found to be linearly correlated with ambient temperatures (P<0.001) in this study. This indicates that the non-equilibrium partitioning of PCDD/Fs in winter may be significantly influenced by the colder temperatures that may have slowed down the exchange between gaseous and particulate fractions.     

Octanol–air partition coefficients of polybrominated biphenyls

The octanol–air partition coefficients (K_OA) for PBB15, PBB26, PBB31, PBB49, PBB103 and PBB153 were determined as a function of temperature using a gas chromatographic retention time technique with 1,1,1-trichloro-2,2-bis (4-chlorophenyl) ethane (p,p′-DDT) as a reference substance. The internal energies of phase change from octanol to air (Δ_OAU) were calculated for the six compounds and were in the range from 74 to 116 kJ mol⁻¹. Simple regression equations of log K_OA versus relative retention times (RRTs) on gas chromatography (GC), and log K_OA versus molecular connectivity indexes (MCI) were obtained, for which the correlation coefficients (r²) were greater than 0.985 at 283.15 K and 298.15 K. Thus the K_OA values of the remaining PBBs can be predicted by using their RRTs and MCI according to these relationships.     

Pesticide residue removal in classic domestic processing of tomato and its effects on product quality

This study was undertaken to evaluate the effectiveness of several household practices (washing with water or acidic, alkaline, and oxidizing solutions, and peeling) in minimizing pesticide residue contamination of tomatoes, as well as the impact on the quality of the treated fruit. Tests were performed using two systemic fungicides (azoxystrobin and difenoconazole) and one contact fungicide (chlorothalonil). Solid-liquid extraction with low temperature partition (SLE/LTP) and liquid-liquid extraction with low temperature partition (LLE/LTP) were used to prepare the samples for pesticides determination by gas chromatography. Washing the tomatoes with water removed approximately 44% of chlorothalonil, 26% of difenoconazole, and 17% of azoxystrobin. Sodium bicarbonate (5%) and acetic acid (5%) solutions were more efficient, removing between 32 and 83% of the residues, while peeling removed from 68 to 88% of the pesticides. The washing solutions altered some fruit quality parameters, including acidity and chroma, and also caused weight loss. Acetic acid (0.15 and 5%) and hypochlorite (1%) solutions had the greatest effect on these parameters.     

Interpreting the relationship between pheromone component emission from commercial lures and captures of Helicoverpa zea (boddie) in bucket and cone traps

Abstract

Male corn earworm moths, Helicoverpa zea (Boddie), were captured in conical Texas pheromone traps (cone traps) and bucket traps baited with four different commercial lures manufactured by three different manufacturers. Because significant numbers were captured in bucket traps baited with some of the lures, and none with others, the volatile emissions from all of the lures were sampled and analyzed by gas Chromatographic methods. The numbers of males captured in two types of trap were compared with bait emissions in an endeavor to define a more effective lure for bucket traps. The lure from one manufacturer captured the same numbers of males in both trap types; one captured more in bucket traps than in cone traps, and another captured only a small number in bucket traps. The emission rate of all active compounds from each of the different lures was approximately linear for the duration of the assays. A gas‐liquid Chromatographic peak associated with a third compound, (Z)‐9‐tetradecenal, which reduces behavioral responses, was observed in the emissions from all lures evaluated. The effectiveness of the Hercon (Emmigsville, PA) lure in capturing males in both types of trap was associated with a lower emission of (Z)‐l 1‐hexadecenal, (Z)‐9‐hexadecenal and (Z)‐9‐tetradecenal than from the other lures.     

Review of advances in the thin layer chromatography of pesticides: 2004–2006

Applications of thin layer chromatography and high performance thin layer chromatography for the separation, detection, and qualitative and quantitative determination of pesticides, other agrochemicals, and related compounds are reviewed for the period from July 1, 2004 to November 1, 2006. Analyses are covered for a variety of samples, such as food, crops, biological, environmental, pharmaceuticals, and formulations, and for residues of pesticides of various types, including insecticides, herbicides, and fungicides, belonging to different chemical classes. In addition to references on residue analysis, studies such as pesticide-structure relationships, metabolism, degradation, and lipophilicity are covered, many of which make use of thin layer radiochromatography.     

Evaluation and validation of two different chromatographic methods (HPLC and LC-MS/MS) for the determination and confirmation of ochratoxin A in pig tissues

This study was undertaken to compare two different analytical methods for the determination and confirmation of ochratoxin A (OTA) in blood serum, kidney and liver of pigs. Sample clean-up was based on liquid-liquid phase extraction. The detection of OTA was accomplished with high-performance liquid chromatography (HPLC) combined either with fluorescence detection (FL) or electro spray ionization (ESI+) tandem mass spectrometry (MS–MS). Comparative method evaluation was based on the investigation of 90 samples of blood serum, kidney and liver per animal originating from different regions of Serbia. The analytical results are discussed in view of the respective method validation data and the corresponding experimental protocols. In general, analytical data obtained with (LC–MS–MS) liquid chromatography electro spray tandem mass spectro metry detection offered comparable good results at the sub-ppb concentration level. The results indicate that the liquid chromatography electro spray tandem mass spectrometric (LC-MS/MS) method was more specific and sensitive for the analysis and confirmation of ochratoxin A in pig tissues then high pressure liquid chromatography (HPLC) method after methylation of OTA.     

气相色谱法测定气田产出水中的甲醇含量

文章建立了使用气相色谱仪分析气田产出水中甲醇含量的方法。通过实验在设定不同分流比的情况下,能有效监测出气田产出水中不同浓度的甲醇含量,此方法灵敏度高,最低检出限为0.02%,测定气田产出水中甲醇加标回收率达到93%～94%。