Spatial gradients and source apportionment of volatile organic compounds near roadways

Concentrations of 55 volatile organic compounds (VOCs) (C₂–C₁₂) are reported near a highway in Raleigh, NC. Thirty-minute samples were collected at eight locations, ranging from approximately 10–100 m perpendicular from the roadway. The highest concentrations of VOCs were generally measured closest to the roadway, and concentrations decreased exponentially with increasing distance from the roadway. The highest mean concentration for individual VOCs were for ethylene (3.10 ppbv) (mean concentration at x = 13 m), propane (2.27 ppbv), ethane (1.91 ppbv), isopentane (1.54 ppbv), toluene (0.95 ppbv), and n-butane (0.89 ppbv). Concentrations at the nearest roadway location (x = 13 m) were generally between 2.0 and 1.5 times those from the farthest roadway location (x = 92 m). The data were apportioned into four source categories using the EPA Chemical Mass Balance Model (CMB8.2): motor vehicle exhaust, compressed natural gas, propane gas, and evaporative gasoline. The majority of the VOCs resulted from motor vehicle exhaust (67 ± 12%) (% of total VOC at x = 13 m ± S.D.). Compressed natural gas, propane gas, and evaporative gasoline accounted for approximately 15%, 7% and 1% of the total VOC emissions, respectively, at x = 13 m.     

Unexpected difference in phenol sorption on PTMA- and BTMA-bentonite

The comparison of phenol sorption on phenyltrimethylammonium (PTMA)- and benzyltrimethylammonium (BTMA)-bentonite shows a clear difference as far as phenol sorption isotherms are concerned. For PTMA-bentonite the sorption isotherm is of a straight-line character which results from simple partitioning of phenol between the aqueous and organic phases sorbed on the bentonite surface. For BTMA-bentonite the isotherm has a convex shape, characteristic of physicochemical sorption.For the first time a three-parametric model, including the dissociation constant of phenol pK_a, distribution constant of phenol Kd_phen and phenolate anion Kd_phen⁻ between the aqueous phase and the bentonite phases is used for the evaluation of phenol sorption on organoclays with pH change. The model shows that the values of Kd_phen are higher than those of Kd_phen⁻ for all investigated initial phenol concentrations.The inspection of the FTIR spectrum of BTMA-bentonite loaded with phenol in the regions 1300–1600 and 1620–1680 cm⁻¹ shows the features of π–π electron interaction between the benzene rings of phenol and the BTMA cation together with the phenol–water hydrogen bond strengthened by this interaction.     

EOX concentrations in sediment in the part of the Bothnian Bay affected by effluents from the pulp and paper mills at Kemi, Northern Finland

The Bothnian Bay, which is the northernmost part of the Gulf of Bothnia in Northern Finland, is affected by effluents discharged from point sources such as the pulp and paper mills of Stora Enso Oyj Veitsiluoto Mill and Oy Metsä-Botnia Ab Kemi Mill at Kemi, and the Kemi municipal sewage plant, as well as the River Kemijoki. In this paper we discuss, how modernisation of the wastewater treatment plant at the mills, and process investments in the Best Available Techniques (BAT) for effluent treatment, have decreased the effluent discharges of biological oxygen demand (BOD), chemical oxygen demand (COD), total phosphorus (Tot-P), total nitrogen (TOT-N), total suspended solids (TSS) and adsorbable organically bound halogens (AOX) from the mills since 1988. One specific aim of the study was to determine the EOX (Extractable Organically Bound Halogens) concentrations in bottom sediment of the Bothnian Bay in order to assess whether the EOX concentrations reflect the reduction in discharges of chlorinated compounds. According to the monitoring program carried out every third year between 1997–2006, the decreasing trend in EOX concentrations in the top 2 cm of the bottom sediment reflect the decrease in organochlorine discharges (AOX) from the mills. In 1997 the EOX concentrations in bottom sediment varied between 3–70 μg of Cl g^?1 (dry weight), and in 2006 between 3.3–32 μg of Cl g^?1 (dry weight).     

Rapid determination of phenolic compounds in water samples by alternating-current oscillopolarographic titration

A rapid, simple and sensitive method was demonstrated for the determination of phenolic compounds in water samples by alternating-current oscillopolarographic titration. With the presence of sulfuric acid, phenol could be transferred into a nitroso-compound by reacting with NaNO2. The titration end-point was obtained by the formation of a sharp cut in the oscillopolarographic with infinitesimal NaNO2 on double platinum electrodes. The results showed that phenol concentration had an excellent linear relationship over the range of 4.82×10-6-9.65×10-3 mol/L, the RSD of the proposed method was lower than 1.5%, and the spiked recoveries of three real water samples were in the range of 95.6%-106.9%.     

Determination of alcohol compounds using corona discharge ion mobility spectrometry

Ion mobility spectrometry （IMS） is a very fast, highly sensitive, and inexpensive technique, it permits efficient monitoring of volatile organic compounds like alcohols. In this article, positive ion mobility spectra for six alcohol organic compounds have been systematically studied for the first time using a high-resolution IMS apparatus equipped with a discharge ionization source. Utilizing protonated water cluster ions （H2O）nH^＋ as the reactant ions and clean air as the drift gas, alcohol organic compounds, ethanol, 1- propanol, 2-propanol, 1-butanol, 1-pentanol and 2-octanol, all exhibit product ion characteristic peaks in their respective ion mobility spectrometry, that is a result of proton transfer reactions between the alcohols and reaction ions （H2O）nH^＋. The mixture of these alcohols, including two isomers, has been detected, and the results showed that they could be distinguished effectively in the ion mobility spectrum. The reduced mobility values have been determined, which are in very well agreement with the traditional ^63Ni-IMS experimental values. The exponential dilution method was used to calibrate the alcohol concentrations, and a detection limit available for the alcohols is in order of magnitude of a few ng/L.     

Anaerobic biodegradation of benzene series compounds by mixed cultures based on optional electronic acceptors

A series of batch experiments were performed using mixed bacterial consortia to investigate biodegradation performance of benzene, toluene, ethylbenzene and three xylene isomers （BTEX） under nitrate, sulfate and ferric iron reducing conditions. The results showed that toluene, ethylbenzene, m-xylene and o-xylene could be degraded independently by the mixed cultures coupled to nitrate, sulfate and ferric iron reduction. Under ferric iron reducing conditions the biodegradation of benzene and p-xylene could be occurred only in the presence of other alkylbenzenes. Alkylbenzenes can serve as the primary subs＇rates to stimulate the transformation of benzene and p-xylene under anaerobic conditions. Benzene and p-xylene are more toxic than toluene and ethylbenzene, under the three terminal electron acceptors conditions, the degradation rates decreased with toluene 〉 ethylbenzene 〉 m-xylene 〉 o-xylene〉 benzene 〉 p- xylene. Nitrate was a more favorable electron acceptor compared to sulfate and ferric iron. The ratio between sulfate consumed and the loss of benzene, toluene, ethylbenzene, o-xylene, m-xylene, p-xylene was 4.44, 4.51, 4.42, 4.32, 4.37 and 4.23, respectively; the ratio between nitrate consumed and the loss of these substrates was 7.53, 6.24, 6.49, 7.28, 7.81, 7.61, respectively; the ratio between the consumption of ferric iron and the loss of toluene, ethylbenzene, o-xylene, m-xylene was 17.99, 18.04, 18.07, 17.97, respectively.     

Thiolsulfonate functionalized polystyrene resin： Preparation and application in the isolation and identification of electrophilic mutagens

A new approach for isolation and identification of elecrtophilic mutagens from complex matrix was developed.Thiosulfonic anion was immobilized onto polystyrene beads and used as separation media.Potassium polystyryl-thiosulfonate,prepared from polystyryl- sulfonyl chloride and KHS,was observed to selectively react with model electrophilic mutagens such as alkyl halides,α-chloroketones andα-chloroesters to produce polystyryl-thiosulfonic esters.After separation from other nonreactive organic compounds,the beads then reacted with ethanethiol to produce unsymmetrical ethyl disulfides which are easily detected by GC/MS.For one mutagenic compound,only one unsymmetrical disulfide was found to contain its structure part.Thus,the structure of the parent mutagens could be deduced from that of the unsymmetrical disulfides.The degree of functionaiization of the potassium polystyryl-thiosulfonate resin was 1.11 mmol/g.Its reactivity was discussed and its recycling method was reported here.     

Analysis of accumulation, extractability, and metabolization of five different phenylarsenic compounds in plants by ion chromatography with mass spectrometric detection and by atomic emission spectroscopy

Phenylated arsenic compounds occur as highly toxic contaminants in former military areas where they were formed as degradation products of chemical warfare agents. Some phenylarsenic compounds such as roxarsone and aminophenylarsonic acids were applied as food additive and veterinary drugs in stock-breeding and therefore pose an environmental risk in agricultural used sites. Very few data exist in the literature concerning uptake and effects of phenylarsenic compounds in plants growing on contaminated soils. In this study, the accumulation, extractability, and metabolization of five different phenylarsenic compounds, phenylarsonic acid, p- and o-aminophenylarsonic acid, phenylarsine oxide, and 3-nitro-4-hydroxyphenylarsonic acid called roxarsone, by the terrestrial plant Tropaeolum majus were investigated. Ion chromatography coupled to inductively coupled plasma mass spectrometry was used to differentiate these arsenic compounds, and inductively coupled plasma atomic emission spectroscopy was used for total arsenic quantification. All compounds considered were taken up by the roots and transferred to stalks, leaves, and flowers. The strongest accumulation was observed for unsubstituted phenylarsonic acid followed by its trivalent analogue phenylarsine oxide that was mostly oxidized in soil whereas the amino- or nitro- and hydroxy-substituted phenylarsonic acids were accumulated to a smaller degree.The highest extraction yield of 90% for ground leaf material was achieved by 0.1 M phosphate buffer, pH 7.7, in a two-step extraction with a total extraction time of 24 h. The extraction of higher amounts of arsenic (50–70% of total arsenic present in leaves depending on arsenic species application) from non-ground intact leaves with deionized water in comparison with the buffer (20–40% of total arsenic) is ascribed to osmotic effects. The arsenic species analysis revealed a cleavage of the amino groups from the phenyl ring for plants treated with aminophenylarsonic acids. A further important metabolic effect consisted in the production of inorganic arsenate and arsenite from the phenylated arsonic acid groups.     

Organotin Compounds and Selected Metals in the Marine Environment of Northern Adriatic Sea

The extent of pollution with organotin compounds and Cd, Pb, Ni, Cu, Zn, Cr, Mn, V, Co and Al was investigated in sediments and mussels (Mytilus galloprovincialis) from the Slovenian costal area of the Northern Adriatic Sea. Sampling was performed in Marina Portorož, Dockyard Izola, non exposed area of the Bay of Mesečev zaliv and in Mariculture Sečovlje. Mussels were taken in the summer and winter time, while sediments were collected during the winter sampling. Organotin compounds were determined by gas chromatography—mass spectrometry and metals by flame or electrothermal atomic absorption spectrometry. The accuracies of the analytical procedures were checked by the analysis of standard reference materials CRM 477 mussel tissue and PACS 2 marine sediment (organotin compounds) and SRM 2976 mussel tissue and CRM 320 river sediment (metals). Good agreements between certified and determined values were obtained. Normalization procedure to Al was applied to estimate the anthropogenic inputs of metals in sediments. The analyses of sediments demonstrated moderate pollution with organotin compounds in Marina Portorož and in Dockyard Izola. Concentrations of tributyltin species were higher than those of dibutyltin and monobutyltin. In mussels substantial contamination with tributyltin was observed in Marina Porotrož and Dockyard Izola. The extent of pollution was higher in the winter time. The analysis of metals in sediments exhibited elevated concentrations in Marina Portorož and Dockyard Izola. Data from the normalization procedure indicated the anthropogenic inputs of Cu, Zn and Cr in Marina Portorož and Mn in Bay of Mesečev zaliv and Dockyard Izola. Mussels, as accumulators of pollutants, in general contained higher metal concentrations during winter time in Dockyard Izola.     

应用ICE和PCA方法评价硝基芳烃的综合毒性

应用种间相关估算(ICE)方法预测50种硝基芳烃缺失的生物毒性数据,对通过ICE计算获得的各种生物毒性数据进行主成分分析(PCA),计算综合毒性因子(ITI),进行综合毒性评价.结果表明,除了黄瓜种子发芽抑制毒性以外,其他各种生物毒性都在1%的显著水平上呈显著的线性正相关.硝基芳烃的这些生物毒性机制基本相似,因此应用ICE方法预测其毒性数据是可行的.QSAR分析表明,ITI与分子最低未占轨道能E_lumo有显著的相关性,r=0.869,表明亲电反应性是硝基芳烃的各种生物毒性所综合反映的主要致毒机理.基于ICE和PCA方法计算得到的ITI与基于QSAR和PCA方法计算得到的ITI的大小趋势具有一致性,ICE与PCA方法的联合应用可以成功地评价和预测硝基芳烃的综合毒性.