A rapid and efficient determination of natural estrogens in soils by pressurised liquid extraction and gas chromatography-mass spectrometry

We present a new analytical procedure for the extraction and determination of natural estrogens in soils based on pressurised liquid extraction and GC-MS determination. After testing twelve solvents, acetone proved to be the most efficient extractant. The optimum extraction temperature is 60 degrees C. Soil extracts have to be purified and concentrated by C-18 solid phase extraction. The dried extracts are derivatised by N-methyl-N-(trimethylsilyl)trifluoro-acetamide before measurement by GC-MS. Recoveries of 79-103% with relative standard deviations 相似文献   

Method development for determination of fluroxypyr in water

Improved methods for extraction and clean up of fluroxypyr residue in water have been established. Two methods of fluroxypyr extraction were used, namely, Direct Measurement of fluroxypyr and Concentration of fluroxypyr onto A Solid Phase Extraction (SPE) Adsorbent, followed by elution with solvent before determination of fluroxypyr. The recovery for Direct Measurement of fluroxypyr in water containing 8-100 microg L(-1), ranged from 86 to 110% with relative standard deviation of 0.7 to 2.15%. For the second method, three types of SPE were used, viz. C18, C18 end-capped and polyvinyl dibenzene (ISOLUTE ENV+). The procedure involved concentrating the analyte from fluroxypyr-spiked water at pH 3, followed by elution of the analyte with 4 mL of acentonitrile. The recovery of fluroxypyr from the spiked sample at 1 to 50 microg L(-1) after eluting through either C18 or C18 end-capped ranged from 40-64% (with relative standard deviation of 0.7 to 2.15) and 41-65% (with standard deviation of 1.52 to 11.9). The use of ISOLUTE ENV+, gave better results than the C18, C18 end-capped or the Direct Measurement Methods. The recovery and standard deviation of fluroxypyr from spiked water using ISOLUTE ENV+ ranged from 91-102% and 2.5 to 5.3, respectively.     

Development of a simple, accurate SPME-based method for assay of VOCs in column breakthrough experiments

Solid-phase microextraction (SPME) with gas chromatography is to be used for assay of effluent liquid samples from soil column experiments associated with VOC fate/transport studies. One goal of the fate/transport studies is to develop accurate, highly reproducible column breakthrough curves for 1,2-cis-dichloroethylene (cis-DCE) and trichloroethylene (TCE) to better understand interactions with selected natural solid phases. For SPME, the influences of the sample equilibration time, extraction temperature and the ratio of volume of sample bottle to that of the liquid sample (V(T)/V(w)) are the critical factors that could influence accuracy and precision of the measured results. Equilibrium between the gas phase and liquid phase was attained after 200 min of equilibration time. The temperature must be carefully controlled due to variation of both the Henry's constant (K(h)) and the fibre/gas phase distribution coefficient (K(fg)). K(h) decreases with decreasing temperature while K(fg) increases. Low V(T)/V(w) yields better sensitivity but results in analyte losses and negative bias of the resultant assay. High V(T)/V(w) ratio yields reduced sensitivity but analyte losses were found to be minimal, leading to better accuracy and reproducibility. A fast SPME method was achieved, 5 min for SPME extraction and 3.10 min for GC analysis. A linear calibration function in the gas phase was developed to analyse the breakthrough curve data, linear between a range of 0.9-236 microgl(-1), and a detection limit lower than 5 microgl(-1).     

Time-integrated sampling of glyphosate in natural waters

Environmental monitoring of pesticide residues in surface water is often done with time-integrated sampling where a specified volume is sampled each hour during, e.g., a week, thus avoiding at momentary high or low extreme concentrations. However, sampling over an extended period of time can result in losses of easily degradable analytes, why the stability of the target analytes over the timespan of the sampling must be checked. Glyphosate is one of the most widely used herbicides. Because of its chemical complexity, glyphosate binds differently to metals and colloids at different pH, and the degradation may also be affected. Recovery of glyphosate from spiked natural waters after 1 and 3 weeks of storage was higher when the samples were acidified to approximately pH 2 rather than at their natural pH. Keeping the samples refrigerated to 4 °C in darkness also enhanced recovery, while glyphosate losses were substantial from samples kept at their natural pH at 20 °C. Total loss of glyphosate was observed in some samples kept at natural pH, 20 °C, and daylight; a loss partly due to binding to metals or colloids that could only partially be reversed by acidification. For 1-week time-integrated sampling a small amount of hydrochloric acid in a piece of heat-sealed hydrophobic micro-porous tubing is added to the sampling bottles before deployment, a procedure that acidifies the samples during collection keeping them below pH 2 until analysis, thus minimising losses of glyphosate. The method also allows determination of the primary degradation product aminomethylphosphonic acid (AMPA).     

Determination of pentachlorophenol (PCP) in waste wood--method comparison by a collaborative trial

Two independently developed and validated procedures for the determination of pentachlorophenol (PCP) in waste wood were compared by means of a collaborative trial. Both methods foresee quantification of PCP by gas chromatography (GC-ECD) after acetylation and differ with regard to the use of methanol or toluene/sulphuric acid, respectively, as solvent in the sonication extraction step. Test samples with established analyte homogeneity were prepared from a ground "real life" starting material. A total of 23 participating laboratories with experience in wood preservative analysis were instructed to apply both methods to three levels of content in the range of 0.5-20 mg PCP/kg. In case of the toluene/sulphuric acid extraction, lower recoveries and higher interlaboratory dispersion of results at the higher PCP contents were observed. Seen against the background of the Horwitz equation a reproducibility standard deviation of approximately 19% for the methanol extraction at the 4.5 mg/kg level meets the requirement for a sound analytical method. Thus, the sonication extraction procedure with methanol has been annexed as a reference method to the German waste wood regulation.     

Preliminary evidence of a decline in perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) concentrations in American Red Cross blood donors

The purpose of this pilot study was to determine whether perfluorooctanesulfonate (PFOS,C(8)F(17)SO(3)(-)) and perfluorooctanoate (PFOA,C(7)F(15)CO(2)(-)) concentrations in American Red Cross blood donors from Minneapolis-St. Paul, Minnesota have declined after the 2000-2002 phase-out of perfluorooctanesulfonyl-fluoride (POSF, C(8)F(17)SO(2)F)-based materials by the primary global manufacturer, 3M Company. Forty donor plasma samples, categorized by age and sex, were collected in 2005, and PFOS and PFOA concentrations were compared to 100 (non-paired) donor serum samples collected in 2000 from the same general population that were analyzed at the time using ion-pair extraction methods with tetrahydroperfluorooctanesulfonate as an internal standard. Eleven of the 100 samples originally collected were reanalyzed with present study methods that involved (13)C- labeled PFOA spiked into the donor samples, original samples, control human plasma, and the calibration curve prior to extraction, and was used as a surrogate to monitor extraction efficiency. Quantification was performed by high performance liquid chromatography tandem mass spectrometry methods. Among the 100 serum samples analyzed for PFOS, the geometric mean was 33.1 ng ml(-1) (95% CI 29.8-36.7) in 2000 compared to 15.1 ng ml(-1) (95% CI 13.3-17.1) in 2005 (p<0.0001) for the 40 donor plasma samples. The geometric mean concentration for PFOA was 4.5 ng ml(-1) (95% CI 4.1-5.0) in 2000 compared to 2.2 ng ml(-1) (95% CI 1.9-2.6) in 2005 (p<0.0001). The decrease was consistent across donors' age and sex. To confirm these preliminary findings, additional sub-sets of year 2000 samples will be analyzed, and a much larger biomonitoring study of other locations is planned.     

Fatal flaws in measuring landfill gas generation rates by empirical well testing

Well testing procedures, such as the Tier 3 methodology specified in the U.S. Code of Federal Regulations (CFR) Subtitle D, are commonly used for directly estimating landfill gas (LFG) emissions at municipal solid waste (MSW) landfills. Similar procedures are also used to estimate LFG generation rates for the design of LFG-to-energy projects. These methodologies assume that the LFG generation rate equals the extraction rate of a test gas well within its radius of influence (ROI). The ROI is defined as the distance from the extraction well at which the induced pressure drop is immeasurable by some standard of precision. Based on fluid dynamic principles, Tier 3 and similar methodologies are demonstrated to be incapable of providing reliable estimates of the LFG generation rate. These tests may either over- or underestimate the LFG generation rate depending on the precision with which the ROI is determined, but they will only coincidentally produce an estimate that accurately represents the actual LFG generation rate. Fluid dynamic principles dictate that the actual LFG generation rate can only be estimated if the pneumatic properties of the refuse and cover materials as well as the excess pressure in the refuse caused by LFG generation are known or can be estimated.     

Sample storage and extraction efficiencies in determination of polycyclic and nitro musks in sewage sludge

Analytical technology is continuously improving, developing better methods for isolating and concentrating trace compounds in environmental samples. Polycyclic and nitro musks (PNMs) are one group of emerging trace compounds detected in municipal wastewater. Differences in sample storage, preparation, and extraction methods for their measurement have led to variability in results. We analyzed 11 PNMs by GC/MS and compared the results of different storage times and extraction methods (supercritical fluid (SFE) or microwave-assisted (MAE)) for 202 samples of primary sludge, waste activated sludge (WAS), raw sludge, and aerobically/anaerobically digested biosolids collected from Canadian municipal wastewater treatment plants. Sixty-three air-dried samples were extracted by SFE, and 139 air-dried, centrifuged, or filtered samples were extracted by MAE. The mean surrogate recoveries were 89% (standard deviation (SD)=11%) for d(10)-anthracene by SFE and 88% (SD=14%) for d(10)-phenanthrene by MAE. Storage study results showed that PNM concentrations changed by a mean of 7% and 9% for primary sludge and WAS respectively after four weeks and decreased up to 25% after 13.5 months of storage in amber glass containers at -18 degrees C. Air-drying of sludge at room temperature caused losses of about 50% of PNM concentrations compared to centrifugation. The proportions of PNMs present in the liquid phase of sludge samples were less than 5% compared to proportions in the sludge solids. The most complete liquid-solid separation was achieved by filtration of frozen/thawed sludge samples, producing a liquid phase that contained less than 1% of the total musk content of the sample.     

Comparison of Laboratory Batch Methods and Large Columns for Evaluating Leachate from Monofilled Solid Wastes

Analyte concentrations in aqueous leachates from polyethylene tanks filled with five different solid wastes were compared with those in extracts from five laboratory batch procedures. Solid wastes used in the study included: electroplating sludge, electric arc furnace dust, paint Incinerator ash, mine tailings, and municipal refuse incinerator ash. Batch extraction procedures used to extract the solid wastes Included: Monofilled Waste Extraction Procedure (MWEP), U.S. EPA Extraction Procedure (EP), Ham Procedure C (HAM-C), Acetate Buffer Extraction Procedure (ABEP), and Saturated Paste Procedure (PASTE).

Analyte concentrations in leachate from the large columns were reproducible and characteristic of each solid waste. In most Instances, analytes in column leachate reached a peak concentration at a liquld-to-solid ratio of 1:1 followed by a gradual to rapid decrease with continued leaching. Analyte concentrations found in large column leachate were related qualitatively to those found in extracts from the batch procedures which used delonlzed water as the extraction medium (i.e., MWEP, HAM-C, and PASTE). Batch extraction procedures using leaching medium containing acetic acid (I.e., EP) or sodium acetate buffer (i.e., ABEP) generally did not reflect analyte concentrations in leachate from the large columns. These results suggest that batch extraction procedures using acetic acid or acetate buffer are less effective for assessing the teachability of monofilled wastes than extraction methods using deionized water as the extraction fluid.     

Analysis of polycyclic aromatic hydrocarbons (PAHs) in airborne particles by direct sample introduction thermal desorption GC/MS

The technique of thermal desorption (TD)–GC/MS was evaluated for measuring airborne, 4–6 ring polycyclic aromatic hydrocarbons (PAHs) collected onto quartz filters. TD provides a more readily automated and sensitive alternative to traditional solvent extraction, decreasing the time/cost of analysis and reducing the risk of analyte loss or sample contamination. The developed method was successfully applied to the analysis of PAH standard solutions loaded on sorbent tubes packed with quartz wool and the graphitized carbon black sorbent Carbograph2. The optimized method showed high desorption efficiency over the whole range of target PAHs with good precision, linearity and sensitivity. The proposed method was verified on an urban dust Standard Reference Material (SRM 1649a); the experimentally determined concentrations agreed with the certified ranges (95% confidence limit) for all target compounds except benzo[a]anthracene, which fell just outside the narrow certified range. The desorption efficiency and the reproducibility of the method was evaluated by analysing pieces of real sample filters sampled from urban air for a period of 24 h. The results confirmed the homogeneity of the filter and showed high recovery efficiencies for all target PAHs.     

Testing the efficiency of extraction of incurred residues from soil with optimized multi-residue method

The reproducibility of extraction of residues from spiked soil samples and from soils containing incurred residues was tested with ¹⁴C-labeled test compounds of different physical-chemical properties. Nearly 100% of the compounds added to the sample before extraction could be recovered with an average reproducibility relative standard deviation (CV) of 5.4%. The additional steps of the determination process (cleanup, evaporation, etc.) contributed to the major part of the variability of the results (CV = 10–20%). The incurred residues were most efficiently extracted with acetone for 30 min followed by the mixture of acetone/ethyl acetate 1:1 for additional 30 min. However, they could only be recovered at various extent (64–90% of total residues), underlying the importance of testing the efficiency of extraction. The residues were identified and quantified by gas chromatography applying thermionic detector. The performance parameters of the method complied with the international method validation guidelines, and they proved to be robust and suitable for determination of pesticide residues in soils of widely different physical–chemical properties.     

Geostatistics as a validation tool for setting ozone standards for durum wheat

Which is the best standard for protecting plants from ozone? To answer this question, we must validate the standards by testing biological responses vs. ambient data in the field. A validation is missing for European and USA standards, because the networks for ozone, meteorology and plant responses are spatially independent. We proposed geostatistics as validation tool, and used durum wheat in central Italy as a test. The standards summarized ozone impact on yield better than hourly averages. Although USA criteria explained ozone-induced yield losses better than European criteria, USA legal level (75 ppb) protected only 39% of sites. European exposure-based standards protected ≥90%. Reducing the USA level to the Canadian 65 ppb or using W126 protected 91% and 97%, respectively. For a no-threshold accumulated stomatal flux, 22 mmol m⁻² was suggested to protect 97% of sites. In a multiple regression, precipitation explained 22% and ozone explained <0.9% of yield variability.     

Application of QuEChERS method and gas chromatography-mass spectrometry for the analysis of cypermethrin residue in milk

Analytical methods for the isolation and determination of cypermethrin in milk, based on the solid-phase microextraction (SPME) and QuEChERS methods (Quick, Easy, Cheap, Effective, Rugged, and Safe) are presented. The SPME technique was not appropriate to analyse cypermethrin in milk, even establishing the best extraction conditions, polydimethylsiloxane fiber, 60 min time extraction, 60 °C temperature extraction, addition of salt (NaCl) and stirring rate. The extraction efficiency was low probably because of the matrix constituents. The QuEChERS method involves the extraction of the analyte with acetonitrile and simultaneous liquid-liquid partitioning formed by adding anhydrous MgSO₄ plus NaCl, followed by the removal of residual water and cleanup using a procedure called dispersive solid-phase extraction, in which anhydrous MgSO₄ plus PSA and C18 are mixed with 1 mL of acetonitrile extract. The detection and quantification limits were 0.01 and 0.04 mg kg^?1, respectively, and the percentage recovery obtained ranged from 92 to 105% with relative standard deviations below 7%.     

Determination of levoglucosan in atmospheric fine particulate matter

A microanalytical method suitable for the quantitative determination of the sugar anhydride levoglucosan in low-volume samples of atmospheric fine particulate matter (PM) has been developed and validated. The method incorporates two sugar anhydrides as quality control standards. The recovery standard sedoheptulosan (2,7-anhydro-beta-D-altro-heptulopyranose) in 20 microL solvent is added onto samples of the atmospheric fine PM and aged for 1 hr before ultrasonic extraction with ethylacetate/ triethylamine. The extract is reduced in volume, an internal standard is added (1,5-anhydro-D-mannitol), and a portion of the extract is derivatized with 10% by volume N-trimethylsilylimidazole. The derivatized extract is analyzed by gas chromatography/mass spectrometry (GC/MS). The recovery of levoglucosan using this procedure was 69 +/- 6% from five filters amended with 2 microg levoglucosan, and the reproducibility of the assay is 9%. The limit of detection is approximately 0.1 microg/mL, which is equivalent to approximately 3.5 ng/m3 for a 10 L/min sampler or approximately 8.7 ng/m3 for a 4 L/min personal sampler (assuming 24-hr integrated samples). We demonstrated that levoglucosan concentrations in collocated samples (expressed as ng/m3) were identical irrespective of whether samples were collected by PM with aerodynamic diameter < or = 2.5 microm or PM with aerodynamic diameter < or = 10 microm impactors. It was also demonstrated that X-ray fluorescence analysis of samples of atmospheric PM, before levoglucosan determinations, did not alter the levels of levoglucosan.     

Decontamination of electronic waste-polluted soil by ultrasound-assisted soil washing

Laboratorial scale experiments were performed to evaluate the efficacy of a washing process using the combination of methyl-β-cyclodextrin (MCD) and tea saponin (TS) for simultaneous desorption of hydrophobic organic contaminants (HOCs) and heavy metals from an electronic waste (e-waste) site. Ultrasonically aided mixing of the field contaminated soil with a combination of MCD and TS solutions simultaneously mobilizes most of polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), and the analyte metal (Pb, Cu, and Ni) burdens. It is found that 15 g/L MCD and 10 g/L TS is an efficient reagent combination reconciling extraction performance and reagent costs. Under these conditions, the removal efficiencies of HOCs and heavy metals are 93.5 and 91.2 %, respectively, after 2 cycles of 60-min ultrasound-assisted washing cycles. By contrast, 86.3 % of HOCs and 88.4 % of metals are removed from the soil in the absence of ultrasound after 3 cycles of 120-min washing. The ultrasound-assisted soil washing could generate high removal efficiency and decrease the operating time significantly. Finally, the feasibility of regenerating and reusing the spent washing solution in extracting pollutants from the soil is also demonstrated. By application of this integrated technology, it is possible to recycle the washing solution for a purpose to reduce the consumption of surfactant solutions. Collectively, it has provided an effective and economic treatment of e-waste-polluted soil.

     

Agriculture as Provider of Both Food and Fuel

A database of global agricultural primary production has been constructed and used to estimate its energy content. The portion of crops available for food and biofuel after postharvest losses was evaluated. The basic conditions for agriculture and plant growth were studied, to ensure sustainable scenarios regarding use of residues. The available energy contents for the world and EU27 was found to be 7,200–9,300 and 430 TWh, respectively, to be compared with food requirements of 7,100 and 530 TWh. Clearly, very little, or nothing, remains for biofuel from agricultural primary crops. However, by using residues and bioorganic waste, it was found that biofuel production could theoretically replace one-fourth of the global consumption of fossil fuels for transport. The expansion potential for global agriculture is limited by availability of land, water, and energy. A future decrease in supply of fossil energy and ongoing land degradation will thus cause difficulties for increased biofuel production from agriculture.     

Pressurised liquid-liquid extraction. An approach to the removal of inorganic non-metal species from used industrial oils

Modified pressurised hot water is used for the development of a high pressure liquid-liquid extraction method for the decontamination of used industrial oils from inorganic non-metal species (chlorine, fluorine and sulphur). The oils were subjected to dynamic extraction with water modified with 5% v/v HNO3 at 200 degrees C as extractant. Under these working conditions the analytes were transferred to the aqueous phase. Spontaneous separation of the two immiscible liquid phases (the used oil and extract) takes place in the collection flask after extraction. The treated and untreated oil samples were oxidised and the chloride, fluoride and sulphate thus formed were determined by ion-chromatography. The method was applied to four oil samples from different locations in Spain. A residence time of approximately =10 min provided oil samples from which 88.3%, 89.4% and 89.4% of chloride, fluoride and sulphate, respectively, have been removed with respect to the initial concentration of each analyte in the oil. The repeatability, expressed as relative standard deviation (RSD), was of 11.9%, 13.7% and 7.2% for Cl(-), F(-) and SO4(2-), respectively; whilst the within-laboratory reproducibility yielded RSDs of 6.2%, 7.9% and 6.2% for the same analytes. The proposed approach has proved to be efficient, simple, easily transferable to industrial scale, cheap, fast and environmentally friendly.     

Determination of 10 particle-associated multiclass polar and semi-polar pesticides from small streams using accelerated solvent extraction

A new analytical method using accelerated solvent extraction was developed for the determination of 10 particle-associated polar and semipolar pesticides. In addition, six deuterated analogues of the target compounds were evaluated as internal standards. The method yielded acceptable accuracy (73–103% recovery) and precision (<25% relative standard deviation) for eight compounds. Using size exclusion chromatography (SEC) as cleanup step resulted in higher recoveries compared to solid phase extraction (SPE) cleanup.

Deuterated standards with 10 or more deuterium atoms performed well as internal standards concerning similar recovery and correlation with the target analytes.

The method was employed to extract particle-associated pesticides from 16 streams located in an area with intense agriculture in France. Acetochlor, pirimicarb, tebuconazole, fenpropidin, -endosulfan and chlorfenvinphos were detected at concentrations up to 1 mg kg⁻¹ dry weight. A comparison with aquatic toxicity data indicated potential risk to the benthic fauna exposed to these concentrations of pirimicarb, -endosulfan and chlorfenvinphos.

We suggest that the method presented here be used for the extraction and quantitation of particle-associated polar pesticides.     

Urban scale modeling of particle number concentration in Stockholm

A three-dimensional dispersion model has been implemented over the urban area of Stockholm (35×35 km) to assess the spatial distribution of number concentrations of particles in the diameter range 3–400 nm. Typical number concentrations in the urban background of Stockholm is 10 000 cm⁻³, while they are three times higher close to a major highway outside the city and seven times higher within a densely trafficked street canyon site in the city center. The model, which includes an aerosol module for calculating the particle number losses due to coagulation and dry deposition, has been run for a 10-day period. Model results compare well with measured data, both in levels and in temporal variability. Coagulation was found to be of little importance in terms of time averaged concentrations, contributing to losses of only a few percent as compared to inert particles, while dry deposition yield particle number losses of up to 25% in certain locations. Episodic losses of up to 10% due to coagulation and 50% due to deposition, are found some kilometers downwind of major roads, rising in connection with low wind speed and suppressed turbulent mixing. Removal due to coagulation and deposition will thus be more significant for the simulation of extreme particle number concentrations during peak episodes.The study shows that dispersion models with proper aerosol dynamics included may be used to assess particle number concentrations in Stockholm, where ultrafine particles principally originate from traffic emissions. Emission factors may be determined from roadside measurements, but ambient temperature must be considered, as it has a strong influence on particle number emissions from vehicles.     

A simple and inexpensive dilution system for the TSI 3007 condensation particle counter

The aim of this study was to develop a dilution system which would permit the TSI 3007 condensation particle counter (CPC) to operate within its maximum detectable concentration threshold, even when sampling extremely high submicron particle concentrations. The intention of this was to provide a better alternative to coincidence correction factors, which have several limitations; the most significant of which being that they are only applicable to a comparatively low concentration and also that the components of the unit are exposed to concentrations beyond their operating specifications. To achieve the aim, a bifurcation-based system was developed and tested repeatedly at concentrations of unleaded petrol combustion particles up to ∼8.5×10⁶ p cm⁻³. The benchmark particle concentration was measured by a TSI 3022A CPC. The results of the tests showed that the nominal dilution ratio based on flow partitioning was applicable up to ∼3.5×10⁵ p cm⁻³, after which particle losses to a capillary tube primarily caused a large increase in apparent dilution. These losses were consistent throughout all tests and allowed the unit to remain below the maximum detection threshold, even under the extreme challenge concentrations encountered. This work represents a useful extension of the operating range of the TSI 3007, without significantly compromising either the quality of data collected or the internal components of the unit.