A photochemical reactor for studies of atmospheric chemistry

A photochemical reactor for studies of atmospheric kinetics and spectroscopy has been built at the Copenhagen Center for Atmospheric Research. The reactor consists of a vacuum FTIR spectrometer coupled to a 100 L quartz cylinder by multipass optics mounted on electropolished stainless steel end flanges, surrounded by UV-A, UV-C and broadband sun lamps in a temperature-controlled housing. The combination of a quartz vessel and UV-C lamps allows higher concentrations of O(¹D) and OH than can be generated by similar chambers. The reactor is able to produce radical concentrations of ca. 8 × 10¹¹ cm^?3 for OH, 3 × 10⁶ cm^?3 for O(¹D), 3.3 × 10¹⁰ cm^?3 for O(³P) and 1.6 × 10¹² cm^?3 for Cl. The reactor can be operated at pressures from 10^?3 to 10³ mbar and temperatures from 240 to 330 K. As a test of the system we have studied the reaction CHCl₃ + Cl using the relative rate technique and find k_CHCl3+Cl/k_CH4+Cl = 1.03 ± 0.11, in good agreement with the accepted value.     

Microenvironmental characteristics important for personal exposures to aldehydes in Sacramento,CA, and Milwaukee,WI

Oxygenated additives in gasoline are designed to decrease the ozone-forming hydrocarbons and total air toxics, yet they can increase the emissions of aldehydes and thus increase human exposure to these toxic compounds. This paper describes a study conducted to characterize targeted aldehydes in microenvironments in Sacramento, CA, and Milwaukee, WI, and to improve our understanding of the impact of the urban environment on human exposure to air toxics. Data were obtained from microenvironmental concentration measurements, integrated, 24-h personal measurements, indoor and outdoor pollutant monitors at the participants' residences, from ambient pollutant monitors at fixed-site locations in each city, and from real-time diaries and questionnaires completed by the technicians and participants. As part of this study, a model to predict personal exposures based on individual time/activity data was developed for comparison to measured concentrations. Predicted concentrations were generally within 25% of the measured concentrations. The microenvironments that people encounter daily provide for widely varying exposures to aldehydes. The activities that occur in those microenvironments can modulate the aldehyde concentrations dramatically, especially for environments such as “indoor at home.” By considering personal activity, location (microenvironment), duration in the microenvironment, and a knowledge of the general concentrations of aldehydes in the various microenvironments, a simple model can do a reasonably good job of predicting the time-averaged personal exposures to aldehydes, even in the absence of monitoring data. Although concentrations of aldehydes measured indoors at the participants' homes tracked well with personal exposure, there were instances where personal exposures and indoor concentrations differed significantly. Key to the ability to predict exposure based on time/activity data is the quality and completeness of the microenvironmental characterizations for the chemicals of interest. Consistent with many earlier studies, personal exposures are difficult to predict using data from regional outdoor monitors.     

An analysis of flaring and venting activity in the Alberta upstream oil and gas industry

Alberta, Canada, is an important global producer of petroleum resources. In association with this production, large amounts of gas (1.14 billion m3 in 2008) are flared or vented. Although the amount of flaring and venting has been measurably reduced since 2002, data from 2005 reveal sharp increases in venting, which have important implications in terms of resource conservation and greenhouse gas emissions (which exceeded 8 million tonnes of carbon dioxide equivalent in 2008). With use of extensive monthly production data for 18,203 active batteries spanning the years 2002-2008 obtained in close cooperation with the Alberta Energy Resources Conservation Board, a detailed analysis has been completed to examine activity patterns of flaring and venting and reasons behind these trends in the Alberta upstream oil and gas industry. In any given year, approximately 6000 batteries reported flaring and/or venting, but the distribution of volumes flared and vented at individual sites was highly skewed, such that small numbers of sites handled large fractions of the total gas flaring and venting in the Province. Examination of month-to-month volume variability at individual sites, cast in terms of a nominal turndown ratio that would be required for a compressor to capture that gas and direct it into a pipeline, further revealed that volumes at a majority of sites were reasonably stable and there was no evidence that larger or more stable sites had been preferentially reduced, leaving potential barriers to future mitigation. Through linking of geospatial data with production data coupled with additional statistical analysis, the 31.2% increase in venting volumes since 2005 was revealed to be predominantly associated with increased production of heavier oils and bitumen in the Lloydminster region of the Province. Overall, the data suggest that quite significant reductions in flaring and venting could be realized by seeking mitigation solutions for only the largest batteries in the Province.     

Accumulation of 14C-trinitrotoluene and related nonextractable (bound) residues in Eisenia fetida

To determine if trinitrotoluene (TNT) forms nonextractable residues in earthworms and to measure the relative degree of accumulation as compared to TNT and its deaminated metabolites, Eisenia fetida was exposed to ¹⁴C-TNT using dermal contact to filter paper or exposure to soil. Nonextractable residues made up 32-68% of total body burden depending on exposure media and depuration time. Parent TNT accounted for less than 3% of radioactivity, while ADNTs accounted for 7-38%. Elimination half-lives were 61-120 h for TNT, ADNTs, and DANTs, which was significantly lower than the half-lives found for nonextractable residues, 201-240 h. However, over 80% of the nonextractable residue was solubilized using weak acid (pH 2). Based on our findings that TNT accumulation occurs primarily as nonextractable residues, which have a longer half-life, and that nonextractable residues can be solubilized, we propose that nonextractable residues could be used as a selective biomarker for assessing TNT contamination.     

Evaporative mass transfer behavior of a complex immiscible liquid

A series of laboratory experiments was conducted with a multiple-component immiscible liquid, collected from the Picillo Farm Superfund Site in Rhode Island, to examine liquid-vapor mass-transfer behavior. The immiscible liquid, which comprises solvents, oils, pesticides, PCBs, paint sludges, explosives, and other compounds, was characterized using gas chromatography and gas chromatography/mass spectrometry to determine mole fractions of selected constituents. Batch experiments were conducted to evaluate equilibrium phase-partitioning behavior. Two sets of air-stripping column studies were conducted to examine the mass-transfer dynamics of five selected target compounds present in the immiscible-liquid mixture. One set of column experiments was designed to represent a system with free-phase immiscible liquid present; the other was designed to represent a system with a residual phase of immiscible liquid. Initial elution behavior of all target components generally appeared to be ideal for both systems, as the initial vapor-phase concentrations were similar to vapor-phase concentrations measured for the batch experiment and those estimated using Raoult's law (incorporating the immiscible-liquid composition data). Later-stage removal of 1,2-dichlorobenzene appeared to be rate limited for the columns containing free-phase immiscible liquid and no porous medium. Conversely, evaporative mass transfer appeared to be ideal throughout the experiment conducted with immiscible liquid distributed relatively uniformly as a residual phase within a sandy porous medium.     

Mercury and other element exposure to tree swallows (Tachycineta bicolor) nesting on Lostwood National Wildlife Refuge, North Dakota

Elevated mercury concentrations in water were reported in the prairie wetlands at Lostwood National Wildlife Refuge, ND. In order to determine whether wildlife associated with these wetlands was exposed to and then accumulated higher mercury concentrations than wildlife living near more permanent wetlands (e.g. lakes), tree swallow (Tachycineta bicolor) eggs and nestlings were collected from nests near seasonal wetlands, semi-permanent wetlands, and lakes. Mercury concentrations in eggs collected near seasonal wetlands were higher than those collected near semi-permanent wetlands or lakes. In contrast, mercury concentrations in nestling livers did not differ among wetland types. Mercury and other element concentrations in tree swallow eggs and nestlings collected from all wetlands were low. As suspected from these low concentrations, mercury concentrations in sample eggs were not a significant factor explaining the hatching success of the remaining eggs in each clutch.     

Enhanced removal of heavy metals in primary treatment using coagulation and flocculation.

The goal of this study was to determine the removal efficiencies of chromium, copper, lead, nickel, and zinc from raw wastewater by chemically enhanced primary treatment (CEPT) and to attain a total suspended solids removal goal of 80%. Operating parameters and chemical doses were optimized by bench-scale tests. Locally obtained raw wastewater samples were spiked with heavy metal solutions to obtain representative concentrations of metals in wastewater. Jar tests were conducted to compare the metals removal efficiencies of the chemical treatment options using ferric chloride, alum, and anionic polymer. The results obtained were compared with those from other studies. It was concluded that CEPT using ferric chloride and anionic polymer is more effective than CEPT using alum for metals removal. The CEPT dosing of 40 mg/L ferric chloride and 0.5 mg/L polymer enhanced heavy metals removal efficiencies by over 200% for chromium, copper, zinc, and nickel and 475% for lead, compared with traditional primary treatment. Efficient metals capture during CEPT can result in increased allowable headworks loadings or lower metal levels in the outfall.     

对美国格林威治湾底栖动物造成危害的潜在胁迫因子的诊断

格林威治湾是纳拉甘西特湾一处受到多种影响因子作用的城市化形成港湾。本研究鉴定了对于格林威治湾底栖动物的重要影响因素。首先利用现存数据与信息来验证水体受损情况。其次确定了影响来源,影响因素和具体影响的存在。继而探究了来源,影响因素和具体影响之间的关系。这使我们能够鉴定出最可能危害水体的影响因素。本研究评估了化学制品、营养物质和悬浮沉积物3类污染物。这种证据权重的方法表明格林威治湾主要受到富营养化相关的影响因素危害。格林威治湾的沉积物富含碳,低溶解氧浓度的情况十分常见,尤其在格林威治湾西部。底栖生物群落出现发育不良的情况,与在氧气不足情况下的预测结果吻合。尽管我们的分析表明环境中的污染物浓度可能导致有害结果的出现,我们并未在结果中检出毒性。这是由于沉积物中存在大量的有机物,这些有机物限制了污染物的生物可利用性。我们的分析还表明悬浮沉积物的影响对于湾区的大部分区域而言几乎不存在。本分析展示了诊断法步骤可以用于组织和评估影响格林威治湾生态健康的潜在影响因素。诊断法步骤对于管理受到多重因素影响的水体非常有用。
精选自Marguerite Pelletier, Kay Ho, Mark Cantwell, Monique Perron, Kenneth Rocha, Robert M. Burgess, Roxanne Johnson, Kenneth Perez, John Cardin, Michael A. Charpentier. Diagnosis of potential stressors adversely affecting benthic invertebrate communities in Greenwich Bay, Rhode Island, USA. Environmental Toxicology and Chemistry: Volume 36, Issue 2, pages 449–462, July 2017. DOI: 10.1002/etc.3562
详情请见http://onlinelibrary.wiley.com/wol1/doi/10.1002/etc.3562/full
     

Evaluating Links Between Forest Harvest and Stream Temperature Threshold Exceedances: The Value of Spatial and Temporal Data

We present the results of a replicated before‐after‐control‐impact study on 33 streams to test the effectiveness of riparian rules for private and State forests at meeting temperature criteria in streams in western Oregon. Many states have established regulatory temperature thresholds, referred to as numeric criteria, to protect cold‐water fishes such as salmon and trout. We examined across‐year and within‐year patterns of exceedance at control and treatment stream temperature probes. Determining whether an exceedance at the downstream end of a harvest was unambiguously related to harvest proved surprisingly difficult. The likelihood of a site exceeding its numeric criterion appeared related, in part, to the site's preharvest temperature range. Four control reaches as well as three preharvest treatment reaches exceeded their numeric criteria, necessitating additional analysis to evaluate timber harvest impacts. Nine percent of sites (3 of 33) both exceeded their numeric criteria and exhibited a potential harvest effect (16.7% of private sites [3 of 18], 0% of State sites [0 of 15]). After harvest, exceedances were typically observed in only the first of the two post‐harvest years. These findings highlight the importance of including temporal and spatial controls in temperature assessments of numeric criteria when the assessment's purpose is to determine whether exceedances are related to human activities.     

Development of engine activity cycles for the prime movers of unconventional natural gas well development

With the advent of unconventional natural gas resources, new research focuses on the efficiency and emissions of the prime movers powering these fleets. These prime movers also play important roles in emissions inventories for this sector. Industry seeks to reduce operating costs by decreasing the required fuel demands of these high horsepower engines but conducting in-field or full-scale research on new technologies is cost prohibitive. As such, this research completed extensive in-use data collection efforts for the engines powering over-the-road trucks, drilling engines, and hydraulic stimulation pump engines. These engine activity data were processed in order to make representative test cycles using a Markov Chain, Monte Carlo (MCMC) simulation method. Such cycles can be applied under controlled environments on scaled engines for future research. In addition to MCMC, genetic algorithms were used to improve the overall performance values for the test cycles and smoothing was applied to ensure regression criteria were met during implementation on a test engine and dynamometer. The variations in cycle and in-use statistics are presented along with comparisons to conventional test cycles used for emissions compliance.

Implications: Development of representative, engine dynamometer test cycles, from in-use activity data, is crucial in understanding fuel efficiency and emissions for engine operating modes that are different from cycles mandated by the Code of Federal Regulations. Representative cycles were created for the prime movers of unconventional well development—over-the-road (OTR) trucks and drilling and hydraulic fracturing engines. The representative cycles are implemented on scaled engines to reduce fuel consumption during research and development of new technologies in controlled laboratory environments.