Secondary ozonides of substituted cyclohexenes: a new class of pollutants characterized by collision-induced dissociation mass spectrometry using negative chemical ionization

Recent studies indicate that secondary ozonides of cyclic alkenes are formed in atmospheric reactions and may be relatively stable. The secondary ozonides (SOZs) of cyclohexene (1), 1-methylcyclohexene (2), 4-isopropyl-1-methylcyclohexene (3) and 4-isopropenyl-1-methylcyclohexene (limonene) (4) have been characterized by rapid gas chromatography electron ionization (EI), negative and positive chemical ionization (CI: ammonia, isobutane and methane) and collision-induced dissociation (CID) mass spectrometry. Both EI and positive CI spectra were found unsuitable for reproducible analysis. However, negative CI showed stable (M−H)⁻ ions with minor fragmentation. CID of the (M−H)⁻ ions resulted in simple and reproducible fragmentation patterns for all four SOZs with loss of m/z 18, 44 and 60, tentatively assigned as H₂O, CO₂ and C₂H₄O₂ or CO₃, respectively. Thus, negative CI-MS–MS in combination with rapid gas chromatography is the preferred method for identification of secondary ozonides of cyclohexenes.     

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.     

浅谈串联四极杆质谱（GC—QqQ-MS／MS）在土壤样品有机污染物分析中的应用

建立了ASE-GPC—GC-QqQ—MS／MS测定土壤中17种有机氯农药和19种多氯联苯以及MAE-SPE—GC-QqQ—MS／MS测定土壤中16种多环芳烃和18种邻苯二甲酸酯的方法。多环芳烃和邻苯二甲酸酯定量限在0．02～2．81μg／kg之间,有机氯农药和多氯联苯定量限在0．01～0．51μg/kg之间。样品加标浓度在5μg/kg时多环芳烃和邻苯二甲酸酯的平均回收率在66．6％～122．1％之间,相对标准偏差均小于20％;有机氯农药和多氯联苯平均回收率在79．6％～93．2％之间,相对标准偏差均小于15％。     

Determination of dithiocarbamate fungicide propineb and its main metabolite propylenethiourea in airborne samples

A simple, rapid and sensitive GC–MS method for the determination of dithiocarbamate fungicide propineb [polymeric zinc propylenebis (dithiocarbamate)] and an improved HPLC procedure for the simultaneous determination of its main metabolite, propylenethiourea, and ethylenethiourea, the main metabolite of all ethylenedithiocarbamates, in airborne samples are described. The method for the analysis of propineb involves the evolution of carbon disulfide (CS₂), under acidic conditions in the presence of stannous chloride, extraction of the generated CS₂ into a layer of isooctane which is then analyzed for CS₂ content by GC–MS in SIM mode. Under the optimum conditions, the retention time of CS₂ was 1.89 min and the total time of chromatographic analysis was 5 min. Recoveries from spiking glass microfibre filters (GF/A) and silica gel filters were 86 ± 7 (n = 9) and 89 ± 4 (n = 9), respectively. The limit of detection is 0.7 ng per filter, which is equivalent to about 0.8–1.0 ng m⁻³ in air. In parallel, an HPLC method with ultraviolet detection is presented for the simultaneous analysis of the metabolites. Separation of the two metabolites was attained in less than 5 min. Recoveries from spiking GF/A and silica gel filters for ethylenethiourea were 100 ± 1 (n = 3) and 98 ± 2 (n = 3), respectively, while for propylenethiourea were 102 ± 1 (n = 3) and 98 ± 1 (n = 3), respectively. The detection limits are about 36–43 and 40–49 ng m⁻³ in air for ethylenethiourea and propylenethiourea, respectively. All the analytes spiked in the filters are proven to be stable for more than one month, at −4 °C.     

Characterization of humic substances of different origin by means of mass spectrometry and neural networks

Mass spectrometry fingerprinting of humic acids extracted from different soils has been carried out using laser desorption/ionization mass spectrometry (LDI-TOF MS). LDI-TOF MS provides characteristic mass spectra fingerprints for the humic acids of different origin. The information given in the fingerprints was evaluated for natural grouping trends in the samples by neural networks computing tools, such as self-organizing feature map (SOFM). This approach is efficient for recognizing patterns in the humic acids samples independently of their characteristic variability; variability characterizing natural products such as humic substances. The use of multi-layer perceptron artificial neural networks gave a successful classification of the samples.     

Analysis of a gas-phase partitioning tracer test conducted in an unsaturated fractured-clay formation

The gas-phase partitioning tracer method was used to estimate non-aqueous phase liquid (NAPL), water, and air saturations in the vadose zone at a chlorinated-solvent contaminated field site in Tucson, AZ. The tracer test was conducted in a fractured-clay system that is the confining layer for the underlying regional aquifer. Three suites of three tracers were injected into wells located 14, 24, and 24 m from a single, central extraction well. The tracers comprised noble gases (traditionally thought to be nonsorbing), alkanes (primarily water partitioning), perfluorides (primarily NAPL partitioning), and halons (both NAPL and water partitioning). Observations of vacuum response were consistent with flow in a fractured system. The halon tracers exhibited the greatest amount of retardation, and helium and the perfluoride tracers the least. The alkane tracers were unexpectedly more retarded than the perfluoride tracers, indicating low NAPL saturations and high water saturations. An NAPL saturation of 0.01, water saturation of 0.215, and gas saturation of 0.775 was estimated based on analysis of the suite of tracers comprising helium, perfluoromethylcyclohexane and dibromodifluoromethane, which was considered to be the most robust set. The estimated saturations compare reasonably well to independently determined values.     

冷原子荧光法测定生活垃圾堆肥产品中汞

通过试验研究,建立了用王水消解、冷原子荧光法测定生活垃圾堆肥产品中汞的方法.本方法的检出限为0.006 mg/kg (按称取0.5 g试样消解定容至50 ml计算),用于国内不同地域的堆肥样品测定,其相对标准偏差(RSD)在2.55%～10.7%之间,加标回收率介于91.0%～108.0%,可作为一种较理想的检验堆肥产品质量的方法.     

聚乙烯微塑料对土壤养分和酶活性的影响

微塑料污染对土壤生态系统的威胁引起了广泛关注.为了明确聚乙烯微塑料对土壤性质的影响,通过为期4个月的土壤培养试验,探究不同质量分数（1 %、2.5 %、5 %）和粒径（30目、100目）聚乙烯微塑料对土壤化学性质、养分含量和酶活性的影响.结果表明:①100目2.5 %和5 %微塑料处理显著降低了土壤pH,不同质量分数和粒径聚乙烯微塑料添加对土壤电导率影响不显著.②相比于CK,添加微塑料会不同程度降低土壤速效钾、有效磷和硝态氮含量.添加100目微塑料显著增加了土壤有机质和铵态氮含量.③当微塑料粒径为100目时,相比于CK,不同质量分数处理均显著提高了土壤过氧化氢酶和碱性磷酸酶活性,5 %处理显著降低了土壤蔗糖酶活性.④土壤性质的变化受微塑料质量分数和粒径影响,质量分数越高、粒径越小,影响越显著.综上,聚乙烯微塑料对土壤性质的影响没有预期的明显,未来研究应重点关注不同影响所涉及的机制问题.     

NUTRIENT MASS BALANCE AND TRENDS,MOBILE RIVER BASIN,ALABAMA, GEORGIA,AND MISSISSIPPI1

ABSTRACT: A nutrient mass balance — accounting for nutrient inputs from atmospheric deposition, fertilizer, crop nitrogen fixation, and point source effluents; and nutrient outputs, including crop harvest and storage — was calculated for 18 subbasins in the Mobile River Basin, and trends (1970 to 1997) were evaluated as part of the U.S. Geological Survey National Water Quality Assessment (NAWQA) Program. Agricultural nonpoint nitrogen and phosphorus sources and urban nonpoint nitrogen sources are the most important factors associated with nutrients in this system. More than 30 percent of nitrogen yield in two basins and phosphorus yield in eight basins can be attributed to urban point source nutrient inputs. The total nitrogen yield (1.3 tons per square mile per year) for the Tombigbee River, which drains a greater percentage of agricultural (row crop) land use, was larger than the total nitrogen yield (0.99 tons per square mile per year) for the Alabama River. Decreasing trends of total nitrogen concentrations in the Tombigbee and Alabama Rivers indicate that a reduction occurred from 1975 to 1997 in the nitrogen contributions to Mobile Bay from the Mobile River. Nitrogen concentrations also decreased (1980 to 1995) in the Black Warrior River, one of the major tributaries to the Tombigbee River. Total phosphorus concentrations increased from 1970 to 1996 at three urban influenced sites on the Etowah River in Georgia. Multiple regression analysis indicates a distinct association between water quality in the streams of the Mobile River drainage basin and agricultural activities in the basin.     

Thermal gradient in the vicinity of Kwale/Okpai gas plant,Delta state,Nigeria: Preliminary observations

Environmental Pollution now persist in Nigeria especially the oil-rich regions of Delta State. One of these problems is due to gas flaring. Thermal gradient resulting from the gas flared at Kwale/Okpai gas plant is hereby reported. Surface temperature variations with distance from the flare point were investigated for the four cardinal directions. The results show a surface temperature elevation of about 3.7° C above the mean normal daily temperature within a radius of 270 M. Hence the thermal equilibrium has been altered. This increase in temperature has undesirable effect on man and his environment especially on the socio-economic lives and activities of the inhabitants. It is therefore necessary that Government Agencies empowered to monitor environment such as Federal Environmental Protection Agency (FEPA) should embark on adequate remediation activities in order to stop the environmental degradation before enormous and permanent damage is caused. Furthermore, the companies involved in the gas flaring should be made to be concerned with the danger they may be causing the inhabitants in particular and the populace in general.