Trace level determination of selected sulfonylurea herbicides in wetland sediment by liquid chromatography electrospray tandem mass spectrometry

Sulfonylurea herbicides are widely used in crop production on the Canadian prairies and a portion of these herbicides applied to cropland are inevitably lost to surrounding aquatic ecosystems. Little is known regarding the presence of sulfonylurea herbicides in wetlands located amongst cropland. This paper describes a new analytical method for the extraction and the determination of seven sulfonylurea herbicides (thifensulfuron-methyl, tribenuron-methyl, ethametsulfuron-methyl, metsulfuron-methyl, rimsulfuron, nicosulfuron and sulfosulfuron) in wetland sediment. The method provided > 85% analyte recovery from fortified sediment for six of the seven sulfonylurea herbicides with a limit of quantification (LOQ) of 1.0 μ g kg^{? 1}. Tribenuron-methyl had significantly lower recovery compared to the other six sulfonylurea herbicides (LOQ = 2 μ g kg^{? 1}). Mean recovery standard deviations were < 10%. This methodology was used to quantify sulfonylurea herbicide residues in sediment samples collected from prairie wetlands situated within the agricultural landscape of Saskatchewan and Manitoba, Canada. This is the first-known detection of sulfonylurea herbicide residues in prairie wetland sediments. Ethametsulfuron-methyl, sulfosulfuron and metsulfuron-methyl, the three most environmentally persistent of the seven sulfonylurea herbicides monitored in the surveillance component of this study, were most frequently detected in wetland sediment with mean concentrations ranging from 1.2 to 10 μ g kg^{? 1}.     

Fast determination of phenoxy acid herbicides in carrots and apples using liquid chromatography coupled triple quadrupole mass spectrometry

A fast, simple and inexpensive method has been developed for the analysis of phenoxy acid herbicides: 2,4-dichlorophenoxyacetic acid (2,4-D), 4-chloro-2-methylphenoxyacetic acid (MCPA), 2-(4-chloro-o-tolyloxy)propionic acid (MCPP), 2-(4-aryloxyphenoxy)propionic acid (Fluazifop) and 2-(4-aryloxyphenoxy)propionic acid (Haloxyfop) in carrots and apples by liquid chromatography coupled to triple quadrupole mass spectrometry (LC/MS/MS). The compounds were analyzed by QuEChERS (quick, easy, cheap, effective, rugged, safe) methodology without cleanup.

The recoveries were performed at two spiked levels (0.05 and 0.5 mg/kg) for both matrices with six replicates for each level. The mean recoveries ranged from 70–92% for both apples and carrots. The precision of the method expressed as relative standard deviation (RSD%) was found to be in the range 3–15%. For all compounds, good linearity (r² > 0.99) was obtained over the range of concentration from 0.05 μ g/mL to 0.5 μ g/mL, corresponding to the pesticide concentrations of 0.05 mg/kg and 0.5 mg/kg, respectively. The determination limits (LOQs) ranged from 0.01 ng/mL to 1.3 ng/mL in solvent, whereas, the LOQs calculated in matrix ranged from 0.05 ng/g to 21.0 ng/g for apples and from 0.06 ng/g to 10.2 ng/g for carrots. The developed methodology combines the advantages of both QuEChERS and LC/MS/MS producing a very rapid, sensitive and cheap method useful for the routine analytical laboratories.     

Matrix effects in analysis of dialkyl phosphate metabolites of organophosphate pesticides in urine by gas chromatography/tandem mass spectrometer

Urinary dialkyl phosphate metabolites (DAPs) are used as biomarkers to evaluate human exposure to organophosphate pesticides. The objective was to evaluate potential artifacts in urinary DAPs analysis during sample preparation and method calibration. Diluted urine pools were commonly used to prepare calibration standards to minimize the effects due to the complexity of urine matrix. Matrix effects on measurements of DAPs were evaluated by spiking known amount of standards into distilled water, synthetic urine and diluted urine pool. Different matrices resulted in similar concentrations detected for all target compounds, except dimethylphosphate (DMP) with the deviation of measurement as large as eight times the spiked amount. In this study, we also found that urinary particles, which usually appeared after thawing frozen human urine samples, could affect the measurements of DAPs, especially DMP and diethylthiophosphate (DETP). Results of DAPs measurements in three types of sample matrices, i.e. urine without particles, urine with particles and particles only were compared. DETP could be subject to large error during this preparation step. The use of deuterated and ¹³C₁₂-labeled DAPs as internal standards is also evaluated. Overall, these issues can cause misidentification and inaccuracies, which may significantly affect the data quality.     

基于关联模型的二恶英在线检测研究

为实现二恶英快速检测,指导废物焚烧炉二恶英减排,通过检测生活垃圾焚烧炉烟气中氯苯和二恶英浓度,研究了三氯苯、四氯苯和二恶英之间的关联关系,并利用实验室自行研制的飞行时间质谱仪对烟气样品的三氯苯进行在线检测。结果表明,三氯苯与二恶英毒性当量(I-TEQ)之间存在良好关联性,相关系数(R2)可达到0.89。仪器检测信号强度与三氯苯浓度之间具有良好的线性关系,根据在线检测烟气样品中三氯苯的信号可得到三氯苯浓度,并根据关联模型计算得到二恶英毒性当量值I-TEQ,实现了对烟气样品中二恶英的快速间接测量。     

Detailed analysis of polybrominated biphenyl congeners in bird eggs from Norway

Individual eggs of six species of birds from Norway representing different food chains were analysed for residues of polybrominated biphenyls (PBBs). In all species, the residue pattern was dominated by hexaBBs. The dominating congeners were PBB 153, PBB 154, and PBB 155. Whereas PBB 153 is present in technical hexabromobiphenyl, PBB 154 and PBB 155 are formed by the reductive debromination of decabromobiphenyl. This was evidenced by the detection of several heptaBBs and octaBBs all of which are typical degradation intermediates of PBB 209. Hepta- and octaBBs were more than one order of magnitude less abundant than the hexaBBs. The second most prevailing homologue group was pentaBBs. The most relevant pentabrominated isomers were PBB 99 and PBB 101. Concentrations of the three hexaBBs - PBB 153, PBB 154, and PBB 155 - amounted to 1.3-13 ng/g wet weight or 3-23% of the contamination with polybrominated diphenyl ethers.     

活性炭处理甲苯气体吸附再生实验研究

研究了活性炭对甲苯废气的吸附穿透过程及热空气解吸过程.穿透曲线实验结果表明,在常规空塔气速范围内,传质区高度基本在5.06～9.75 cm,传质区不饱和度在0.4～0.7.在动态运行情况下,活性炭对甲苯的饱和吸附容量在0.16～0.24 g/g.热空气吹脱实验表明,适宜的脱附工况条件为脱附温度180 ℃、脱附空气流速0.106 m/s、脱附时间40 min.     

气浮中离子气团的应用

文章简介了离子气团产生的原理,离子气流发生器的工作原理及离子气团在水处理技术气浮中的应用.     

Carbon source/sink function of a subtropical, eutrophic lake determined from an overall mass balance and a gas exchange and carbon burial balance

Although studies on carbon burial in lake sediments have shown that lakes are disproportionately important carbon sinks, many studies on gaseous carbon exchange across the water-air interface have demonstrated that lakes are supersaturated with CO(2) and CH(4) causing a net release of CO(2) and CH(4) to the atmosphere. In order to more accurately estimate the net carbon source/sink function of lake ecosystems, a more comprehensive carbon budget is needed, especially for gaseous carbon exchange across the water-air interface. Using two methods, overall mass balance and gas exchange and carbon burial balance, we assessed the carbon source/sink function of Lake Donghu, a subtropical, eutrophic lake, from April 2003 to March 2004. With the overall mass balance calculations, total carbon input was 14 905 t, total carbon output was 4950 t, and net carbon budget was +9955 t, suggesting that Lake Donghu was a great carbon sink. For the gas exchange and carbon burial balance, gaseous carbon (CO(2) and CH(4)) emission across the water-air interface totaled 752 t while carbon burial in the lake sediment was 9477 t. The ratio of carbon emission into the atmosphere to carbon burial into the sediment was only 0.08. This low ratio indicates that Lake Donghu is a great carbon sink. Results showed good agreement between the two methods with both showing Lake Donghu to be a great carbon sink. This results from the high primary production of Lake Donghu, substantive allochthonous carbon inputs and intensive anthropogenic activity. Gaseous carbon emission accounted for about 15% of the total carbon output, indicating that the total output would be underestimated without including gaseous carbon exchange.     

Motor Vehicle Contributions to Ambient PM10 and PM2.5 at Selected Urban Areas in the USA

A source apportionment study was carried out to estimate the contribution of motor vehicles to ambient particulate matter (PM) in selected urban areas in the USA. Measurements were performed at seven locations during the period September 7, 2000 through March 9, 2001. Measurements included integrated PM_2.5 and PM₁₀ concentrations and polycyclic aromatic hydrocarbons (PAHs). Ambient PM_2.5 and PM₁₀ were apportioned to their local sources using the chemical mass balance (CMB) receptor model and compared with results obtained using scanning electron microscopy (SEM). Results indicate that PM_2.5 components were mainly from combustion sources, including motor vehicles, and secondary species (nitrates and sulfates). PM₁₀ consisted mainly of geological material, in addition to emissions from combustion sources. The fractional contributions of motor vehicles to ambient PM were estimated to be in the range from 20 to 76% and from 35 to 92% for PM_2.5 and PM₁₀, respectively.     

Watershed Nitrogen and Mercury Geochemical Fluxes Integrate Landscape Factors in Long-term Research Watersheds at Acadia National Park, Maine, USA

This paper is an overview of this special issue devoted to watershed research in Acadia National Park (Acadia NP). The papers address components of an integrated research program on two upland watersheds at Acadia NP, USA (44° 20′ N latitude; 68° 15′ E longitude). These watersheds were instrumented in 1998 to provide a long-term foundation for regional ecological and watershed research. The research was initiated as part of EPA/NPS PRIMENet (Park Research and Intensive Monitoring of Ecosystems Network), a system of UV-monitoring stations and long-term watershed research sites located in US national parks. The initial goals at Acadia NP were to address research questions about mercury, acid rain, and nitrogen saturation developed from prior research. The project design was based on natural differences in forests and soils induced by an intense wildfire in one watershed in 1947. There is no evidence of fire in the reference watershed for several hundred years. We are testing hypotheses about controls on surface water chemistry, and bioavailability of contaminants in the contrasting watersheds. The unburned 47-ha Hadlock Brook watershed is 70% spruce-fir mature conifer forest. In contrast, burned 32-ha Cadillac Brook watershed, 4 km northeast of the Hadlock watershed, is 20% regenerating mixed northern hardwoods and 60% shrub/rocky balds. Differences in atmospheric deposition are controlled primarily by forest stand composition and age. The watersheds are gauged and have water chemistry stations at 122 m (Cadillac) and 137 m (Hadlock); watershed maximum elevations are 468 and 380 m, respectively. The stream water chemistry patterns reflect, in part, the legacy of the intense fire, which, in turn, controls differences in forest vegetation and soil characteristics. These factors result in higher nitrogen and mercury flux from the unburned watershed, reflecting differences in atmospheric deposition, contrasting ecosystem pools of nitrogen and mercury, and inferred differences in internal cycling and bioavailabilty.