Microscale analytical methods for the quantitative detection of PCBs and PAHs in small tissue masses

Microscale methods (MM) were evaluated and compared to traditional methods (TM) for measuring polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) in spiked and standard reference fish and mussel tissues. MMs are advantageous because they use small tissue masses (ca. 100 mg), and maintain sensitivity through reducing final extract volume (traditionally 1 ml) by an order of magnitude or more (40 μl—PCBs; 100 μl—PAHs). Procedural losses occurred in the MMs’ combined cleanup/primary evaporation step (19% PAHs; 6% PCBs), and the final extract concentration (14% PAHs; 22% PCBs). The PAH MM performed comparably to the TM. Although most PCBs had recoveries >50%, the PCB MM generally yielded lower recoveries than the TM. Average method detection limits were 0.6 μg/kg (TM) and 1.0 μg/kg (MM) for PCBs and 25.7 μg/kg (TM) and 27.7 μg/kg (MM) for PAHs. MMs described for PCB and PAH tissue samples are potentially viable alternatives to TMs, and could lead to cost savings in bioaccumulation/toxicity tests.     

Alternative methods for the pilot-scale production and characterization of chitosan nanoparticles

Environmental Science and Pollution Research - This work describes the production/characterization of low molar mass chitosan nanoparticles derived from waste shrimp shells (SSC), as well as from a...     

Optimization of analytical methods to improve detection of erythromycin from water and sediment

Analytical methods to improve the detection of erythromycin in water and sediment were developed to optimize for erythromycin's recovery of extractable and bound residues from the aquatic environment. The objective of this study was to determine optimal recovery of erythromycin from water and sediment to improve its detection in environmental samples through solid-phase extraction (SPE) and sediment-extraction methods. SPE methods examined included previously reported methods for macrolide and sulfonamide antibiotics with erythromycin recoveries ranging from 75.5 % to 94.7 %. Extraction of erythromycin was performed from sand employing various solvents and buffers to determine the best method for extraction from two sandy loam pond sediments. Various extraction times were also examined, and all extraction procedures were performed in duplicate. The greatest recovery of (14)C-erythromycin in the Iowa sediment was 84 % using 0.3 M ammonium acetate at pH 4.2: acetonitrile (15:85, v/v) solution. The Oklahoma sediment yielded the greatest recovery of (14)C-erythromycin at 86.7 % with 0.3 M ammonium acetate at pH 7: acetonitrile (30:70, v/v) with a 60-minute shake time. The present results demonstrate improved extraction methods for enhancing the accuracy of erythromycin detection from environmental samples.     

Optimization of analytical methods to improve detection of erythromycin from water and sediment

Analytical methods to improve the detection of erythromycin in water and sediment were developed to optimize for erythromycin's recovery of extractable and bound residues from the aquatic environment. The objective of this study was to determine optimal recovery of erythromycin from water and sediment to improve its detection in environmental samples through solid-phase extraction (SPE) and sediment-extraction methods. SPE methods examined included previously reported methods for macrolide and sulfonamide antibiotics with erythromycin recoveries ranging from 75.5 % to 94.7 %. Extraction of erythromycin was performed from sand employing various solvents and buffers to determine the best method for extraction from two sandy loam pond sediments. Various extraction times were also examined, and all extraction procedures were performed in duplicate. The greatest recovery of ¹⁴C-erythromycin in the Iowa sediment was 84 % using 0.3 M ammonium acetate at pH 4.2: acetonitrile (15:85, v/v) solution. The Oklahoma sediment yielded the greatest recovery of ¹⁴C-erythromycin at 86.7 % with 0.3 M ammonium acetate at pH 7: acetonitrile (30:70, v/v) with a 60-minute shake time. The present results demonstrate improved extraction methods for enhancing the accuracy of erythromycin detection from environmental samples.     

A review of the main methods for composite adsorbents characterization

Environmental Science and Pollution Research - Adsorption is a promising technology for removing several contaminants from aqueous matrices. In the last years, researchers worldwide have been...     

Sampling and analytical methods for assessing the levels of organic pollutants in the atmosphere: PAH, phthalates and psychotropic substances: a short review

This short review presents the procedures used to monitor PAHs, phthalates and psychotropic substances in the air, and the results of some measurements made in Italy and abroad. Organic contaminants are characterized by a variety of physical and chemical properties, including aggregation phase, concentration level, and life time. This variety widens the spectrum of procedures developed to assess their occurrence in the environment and biota, but prevents the complete speciation of the "organic fraction" of air, waters and particulates, and attention is paid to a few substances. The progress in health sciences stimulates the concern on contaminants and the development of new instrumental apparatuses and methods; new chemicals are continuously identified or recognized as capable of injuring the environment and organisms. Persistent organic pollutants and persistent biologically active toxicants are subject to regulation and extensively measured by means of standard procedures. For instance, polycyclic aromatic hydrocarbons, polychlorobiphenyls and polychlorodibenzodioxins are recovered from air through phase partition, thermal desorption or solvent extraction, then separated and detected through GC-MS or HPLC-MS procedures. By contrast, dedicated methods must be still optimized to monitor candidates or possible candidates as emerging organic pollutants, e.g. phthalates, flame retardants and perfluoroalkanes. Also, psychotropic substances appear of potential concern. Legal and illicit substances are commonly detected in the urban air besides waste and surface waters. If nicotine, caffeine and cocaine will result to enough persistence in the air, their monitoring will become an important issue of global chemical watching in the next future.     

Camphor wood,a potentially harmful museum storage material: an analytical study using instrumental methods

Environmental Science and Pollution Research - Camphor wood is welcomed by museums due to its insect-repelling effect but the smell indicates a potential risk to the collections. In order to judge...     

PM2.5 characterization for time series studies: Pointwise uncertainty estimation and bulk speciation methods applied in Denver

Many studies have identified associations between adverse health effects and short-term exposure to particulate matter less than 2.5 μm in diameter (PM_2.5). These effects, however, are not consistent across geographical regions. This may be due in part to variations in the chemical make-up of PM_2.5 resulting from unique combinations of sources, both primary and secondary, in different regions. The Denver Aerosol Sources and Health (DASH) study is a multi-year time series study designed to characterize the daily chemical composition of PM_2.5 in Denver, identify the major contributing sources, and investigate associations between sources and a broad array of adverse health outcomes.Measurement methodology, field blank correction, pointwise uncertainty estimation and detection limit consideration are discussed in the context of bulk speciation for the DASH study. Results are presented for the first 4.5 years of mass, inorganic ion and bulk carbon speciation. The derived measurement uncertainties were propagated using the root sum of squares method and show good agreement with precision estimates derived from bi-weekly duplicate samples collected on collocated samplers. Gravimetric mass has the most uncertainty of any measurement and reconstructed mass generated from the sum of the individual species shows less uncertainty than measured mass on average. The methods discussed provide a good framework for PM_2.5 speciation measurements and are generalizable to analysis of other environmental measures.     

Bacterial toxicity comparison between nano- and micro-scaled oxide particles

Toxicity of nano-scaled aluminum, silicon, titanium and zinc oxides to bacteria (Bacillus subtilis, Escherichia coli and Pseudomonas fluorescens) was examined and compared to that of their respective bulk (micro-scaled) counterparts. All nanoparticles but titanium oxide showed higher toxicity (at 20 mg/L) than their bulk counterparts. Toxicity of released metal ions was differentiated from that of the oxide particles. ZnO was the most toxic among the three nanoparticles, causing 100% mortality to the three tested bacteria. Al₂O₃ nanoparticles had a mortality rate of 57% to B. subtilis, 36% to E. coli, and 70% to P. fuorescens. SiO₂ nanoparticles killed 40% of B. subtilis, 58% of E. coli, and 70% of P. fluorescens. TEM images showed attachment of nanoparticles to the bacteria, suggesting that the toxicity was affected by bacterial attachment. Bacterial responses to nanoparticles were different from their bulk counterparts; hence nanoparticle toxicity mechanisms need to be studied thoroughly.     

A combined approach of physicochemical and biological methods for the characterization of petroleum hydrocarbon-contaminated soil

Main physicochemical and microbiological parameters of collected petroleum-contaminated soils with different degrees of contamination from DaGang oil field (southeast of Tianjin, northeast China) were comparatively analyzed in order to assess the influence of petroleum contaminants on the physicochemical and microbiological properties of soil. An integration of microcalorimetric technique with urease enzyme analysis was used with the aim to assess a general status of soil metabolism and the potential availability of nitrogen nutrient in soils stressed by petroleum-derived contaminants. The total petroleum hydrocarbon (TPH) content of contaminated soils varied from 752.3 to 29,114 mg kg^?1. Although the studied physicochemical and biological parameters showed variations dependent on TPH content, the correlation matrix showed also highly significant correlation coefficients among parameters, suggesting their utility in describing a complex matrix such as soil even in the presence of a high level of contaminants. The microcalorimetric measures gave evidence of microbial adaptation under highest TPH concentration; this would help in assessing the potential of a polluted soil to promote self-degradation of oil-derived hydrocarbon under natural or assisted remediation. The results highlighted the importance of the application of combined approach in the study of those parameters driving the soil amelioration and bioremediation.     

PM2.5 characterization for time series studies: Organic molecular marker speciation methods and observations from daily measurements in Denver

Particulate matter less than 2.5 microns in diameter (PM_2.5) has been shown to have a wide range of adverse health effects and consequently is regulated in accordance with the US-EPA's National Ambient Air Quality Standards. PM_2.5 originates from multiple primary sources and is also formed through secondary processes in the atmosphere. It is plausible that some sources form PM_2.5 that is more toxic than PM_2.5 from other sources. Identifying the responsible sources could provide insight into the biological mechanisms causing the observed health effects and provide a more efficient approach to regulation. This is the goal of the Denver Aerosol Sources and Health (DASH) study, a multi-year PM_2.5 source apportionment and health study.The first step in apportioning the PM_2.5 to different sources is to determine the chemical make-up of the PM_2.5. This paper presents the methodology used during the DASH study for organic speciation of PM_2.5. Specifically, methods are covered for solvent extraction of non-polar and semi-polar organic molecular markers using gas chromatography–mass spectrometry (GC–MS). Vast reductions in detection limits were obtained through the use of a programmable temperature vaporization (PTV) inlet along with other method improvements. Results are presented for the first 1.5 years of the DASH study revealing seasonal and source-related patterns in the molecular markers and their long-term correlation structure. Preliminary analysis suggests that point sources are not a significant contributor to the organic molecular markers measured at our receptor site. Several motor vehicle emission markers help identify a gasoline/diesel split in the ambient data. Findings show both similarities and differences when compared with other cities where similar measurements and assessments have been made.     

空气中挥发性有机物监测技术的研究进展

讨论了空气中挥发性有机化合物（VOCs）的监测分析方法研究进展。重点介绍了空气中VOCs的采集、分析和测定;简要叙述了样品前处理的新方法--固相微萃取法（SPME）与其它前处理方法的研究概况。     

Positive vs. false detection: A comparison of analytical methods and performance for analysis of cyclic volatile methylsiloxanes (cVMS) in environmental samples from remote regions

Contamination and analytical variation can significantly hinder trace analysis of cyclic methyl volatile siloxanes (cVMS); potentially resulting in the report of false positives at concentrations approaching detection limits. To assess detection and variation associated with trace cVMS analysis in environmental matrices, a co-operative laboratory comparison for the analysis of octametylcyclotetrasiloxane (D4), decamethylcylcopentasiloxane (D5), and dodecametylcyclohexasiloxane (D6) in sediment and biota from the Svalbard Archipelago was conducted. Two definitions of detection limits were evaluated in this study; method detection limits (MDL, matrix defined) and limits of detection (LOD, solvent defined). D5 was the only cVMS detected above both LOD (0.08–0.81 ng g⁻¹ ww) and MDL (0.47–2.36 ng g⁻¹ ww) within sediment by all laboratories where concentrations ranged from 0.55 to 3.91 ng g⁻¹ ww. The percentage of positive detects for D5 decreased by 80% when MDL was defined as the detection limit. D5 was also detected at the highest frequency among all laboratories in fish liver with concentrations ranging from 0.72 to 345 ng g⁻¹ ww. Similar to sediment, percentage of positive detects for D5 decreased by 60% across all laboratories for fish livers when using MDL (0.68–3.49 ng g⁻¹ ww). Similar observations were seen with both D4 and D6, indicating that sample matrix significantly contributes to analytical response variation. Despite differences in analytical methods used between laboratories, good agreement was obtained when using MDL to define detection limits. This study shows the importance of incorporating variation introduced by sample matrices into detection limit calculations to insure data accuracy of cVMS at low concentrations.     

Assessment of elemental composition and properties of copper smelter-affected dust and its nano- and micron size fractions

A comprehensive approach has been developed to the assessment of composition and properties of atmospherically deposited dust in the area affected by a copper smelter. The approach is based on the analysis of initial dust samples, dynamic leaching of water soluble fractions in a rotating coiled column (RCC) followed by the determination of recovered elements and characterization of size, morphology and elemental composition of nano-, submicron, and micron par ticles of dust separated using field-flow fractionation in a RCC. Three separated size fractions of dust (<0.2, 0.2–2, and >2 μm) were characterized by static light scattering and scanning electron microscopy, whereupon the fractions were analyzed by ICP-AES and ICP-MS (after digestion). It has been evaluated that toxic elements, which are characteristics for copper smelter emissions (As, Cu, Zn), are accumulated in fraction >2 μm. At the same time, up to 2.4, 3.1, 8.2, 6.7 g/kg of As, Cu, Zn, Pb, correspondently, were found in nanoparticles (<0.2 μm). It has been also shown that some trace elements (Sn, Sb, Ag, Bi, and Tl) are accumulated in fraction <0.2, and their content in this fraction may be one order of magnitude higher than that in the fraction >2 μm, or the bulk sample. It may be assumed that Sn, Sb, Ag, Bi, Tl compounds are adsorbed onto the finest dust particles as compared to As, Cu, Zn compounds, which are directly emitted from the copper smelter as microparticles.

     

Evaluation of methods for the physical characterization of the fine particle emissions from two residential wood combustion appliances

The fine particle emissions from a U. S. certified non-catalytic wood stove and a zero-clearance fireplace burning Quercus rubra L. (northern red oak) and Pseudotsuga menziesii (Douglas fir) cordwood each at two different moisture levels were determined. Emission testing was performed using both time-integrated and continuous instrumentation for total particle mass, particle number, particle size distribution, and fixed combustion gases using an atmospheric wind tunnel, full-flow laboratory dilution tunnel, and dilution stack sampler with a comparison made between the three dilution systems and two sampling filter types. The total mass emission factors (EFs) for all dilution systems and filter media are extremely variable ranging from <1 to 55 g kg⁻¹ of dry wood depending on the combination of appliance type, wood species and moisture content, filter medium, and dilution system. For Teflon filter sampling of stove emissions in the wind tunnel, the total mass EFs varied from 2 to 8 g kg⁻¹ of dry fuel depending on wood type whereas the equivalent fireplace emissions burning wet oak averaged 11 g kg⁻¹. A substantial number of ultrafine particles in the accumulation size range were also observed during all tests as determined by an Electrical Low Pressure Impactor (ELPI) and Scanning Mobility Particle Sizer. The PM-2.5 (particles ≤2.5 μm in aerodynamic diameter) fractions determined from the ELPI electrometer data ranged from 93 to 98% (mass) depending on appliance type as reported previously by Hays et al. (Aerosol Science, 34, 1061, 2003).     

Innovative methods for emission inventory development and evaluation: workshop summary

Emission inventories are an essential tool for evaluating, managing, and regulating air pollution. Refinements and innovations in instruments that measure air pollutants, models that calculate emissions, and techniques for data management and uncertainty assessment are needed to enhance emission inventories. This workshop provided recommendations for improving emission factors, improving emission models, and reducing inventory uncertainty. Communication that increases cooperation between developers and users of inventories is essential. Emission inventories that incorporate these improvements will meet the challenges of the future.     

Reduction of sampling and analytical errors for electron microscopic analysis of atmospheric aerosols

Electron microscopy-energy dispersive spectroscopy (EM/EDS) can be used to determine the elemental composition of individual particles. However, the accuracy with which atmospheric particle compositions can be quantitatively determined is not well understood. In this work we explore sources of sampling and analytical bias and methods of reducing bias. Sulfuric acid [H₂SO₄] and ammonium sulfate [(NH₄)₂SO₄] particles were collected on beryllium, silicon, and carbon substrates with similar deposition densities. While [(NH₄)₂SO₄] particles were observed on all substrates, [H₂SO₄] and ammonia-treated [H₂SO₄] particles could not be found on beryllium substrates. Interactions between the substrate and sulfuric acid particles are implicated. When measured with EM/EDS, [H₂SO₄] particles exposed to ammonia overnight were found having lower beam damage rates (0.000 ± 0.002 fraction s⁻¹) than those without any treatment (0.023 ± 0.006 fraction s⁻¹) For laboratory-generated [C₁₀H₆(SO₃Na)₂] particles, the composition determined using the experimental k-factors evaluated from independent particle standards of similar composition and size shows an error less than 20% for all constituents, while greater than 78% errors were found when k-factors were calculated from the theory. This study suggests (1) that sulfate beam damage can be reduced by exposure of atmospheric particle samples to ammonia before analysis, (2) that beryllium is not a suitable substrate for atmospheric particle analysis, and (3) calibration (k-factor determination) using particle standards of similar size and composition to particles present in the atmosphere shows promise as a way of improving the accuracy of quantitative EM analysis.     

垃圾降解过程中淀粉酶活性测定条件优化

垃圾填埋场中垃圾降解初期,淀粉酶活性对于垃圾填埋场中碳素的转化过程和垃圾填埋场生物学特性的研究有重要意义,而且也可作为垃圾填埋场稳定化机制研究的重要指标之一.以模拟垃圾填埋系统的垃圾为研究对象,通过正交实验(L25(56))对淀粉酶活性的测定条件进行了优化研究.结果表明:(1)正交实验结果表明,对淀粉酶活性测定的影响大...