Degradation of picric acid and 2,6-DNT in marine sediments and waters: the role of microbial activity and ultra-violet exposure

Bio- and photo-transformation of two munitions and explosives of concern, 2,6-dinitrotoluene (2,6-DNT) and 2,4,6-trinitrophenol (picric acid) were assessed in spiked marine sediments and water. A sandy and a fine-grained sediment, with 0.25% and 1.1% total organic carbon, respectively, were used for biotransformation assessments at 10 and 20 degrees C. Sterilized sediments were used as controls for biotic vs. abiotic transformation. Transformation products were analyzed by HPLC, GC/MS and LC/MS. Biotransformation in sediments started soon after the initial contact of the chemicals with the sediments and proceeded for several months, with rates in the following sequence: fine-grain at 20 degrees C > fine-grain at 10 degrees C > sand at 20 degrees C > sand at 10 degrees C. The biotransformation paths seemed to be similar for all conditions. The major biotransformation product of 2,6-DNT was 2-amino-6-nitrotoluene (2-A-6-NT). 2-Nitrotoluene (2-NT) and other minor components, including N,N-dimethyl-3-nitroaniline, benzene nitrile, methylamino-2-nitrosophenol and diaminophenol, were also identified. After more prolonged incubation these chemicals were replaced by high molecular weight polymers. Several breakdown products of picric acid were identified by GC/MS, including 2,4-dinitrophenol, amino dinitrophenols, 3,4-diamino phenol, amino nitrophenol and nitro diaminophenol. Photo-transformation of 2,6-DNT and picric acid in seawater was assessed under simulated solar radiation (SSR). No significant photolysis of picric acid in seawater was observed for up to 47 days, but photo-transformation of 2,6-DNT began soon after the initial exposure to SSR, with 89% being photo-transformed in 24 h and none remaining after 72 h. High molecular weight chemicals were generated, with mass spectra ranging from molecular weight 200-500 compared to 182 for DNT, and the color of the stock solution changed from clear to orange. Complexity of the mass spectra and mass differences among fragments suggest that multiple polymers were produced and were co-eluting during the LC/MS analyses.     

Trends and variability of ground-level O3 in Connecticut over the period 1981-1997

The temporal and spatial characteristics of ground-level (tropospheric) O3 measured at 10 monitoring stations in Connecticut were studied from 1981 to 1997. To detect the O3 trend caused by changes in precursor emissions, moving average filters and a linear least-squared regression model were used to eliminate the short-term variation and effects of temperature from raw time-series O3 data. The results showed a significant decrease in the number of days exceeding the National Ambient Air Quality Standards (NAAQS) and a small change in total O3 concentration. The analysis indicated that the variation of daily maximum O3, caused by changes in emissions, explained more than 10% of the total O3 variation in Bridgeport and East Hartford during the past 17 years. Meanwhile, a strong weekly cycle was also found in O3 time-series data, resulting in lower O3 concentration in urban areas than in nonurban areas, implying that land use and land cover have impacts on the spatial distribution of ground-level O3 in Connecticut.     

Emissions of sulfur trioxide from coal-fired power plants

Emissions of sulfur trioxide (SO3) are a key component of plume opacity and acid deposition. Consequently, these emissions need to be low enough to not cause opacity violations and acid deposition. Generally, a small fraction of sulfur (S) in coal is converted to SO3 in coal-fired combustion devices such as electric utility boilers. The emissions of SO3 from such a boiler depend on coal S content, combustion conditions, flue gas characteristics, and air pollution devices being used. It is well known that the catalyst used in the selective catalytic reduction (SCR) technology for nitrogen oxides control oxidizes a small fraction of sulfur dioxide in the flue gas to SO3. The extent of this oxidation depends on the catalyst formulation and SCR operating conditions. Gas-phase SO3 and sulfuric acid, on being quenched in plant equipment (e.g., air preheater and wet scrubber), result in fine acidic mist, which can cause increased plume opacity and undesirable emissions. Recently, such effects have been observed at plants firing high-S coal and equipped with SCR systems and wet scrubbers. This paper investigates the factors that affect acidic mist production in coal-fired electric utility boilers and discusses approaches for mitigating emission of this mist.     

天目湖沙河水库热分层变化及其对水质的影响

为揭示亚热带水库热分层的季节性变化特征、影响因素及水质效应,以最大水深11 m的江苏溧阳天目湖沙河水库为例,基于对水库坝前区(TM1)3~11月逐时的水温监测及对该水库2009~2016年相关水质和气象指标监测,分析了该水库热分层的形成和消失时间、驱动因素及其对水质的影响.结果表明,天目湖沙河水库呈典型的亚热带单循环混合模式:春季随着太阳辐射的增强,水温逐渐升高,当表层水温升至21℃左右时,热分层稳定形成,在整个5~9月期间水体热分层十分稳定;秋季随着太阳辐射的减弱,水温逐渐降低,当表层水温降至19℃左右时,热分层基本消失,在10~4月期间水体呈混合状态.热分层期间,表层和底层的水温差随太阳辐射的增强而增加;日均气温超过30℃的情况下,水体热分层更加稳定;夏季强降雨过程降低了水体表层的温度、减弱了上层5 m水体的温度分层,但对5 m以下深度的热分层状况基本无影响.水温分层对水库水质产生一定的影响:热分层期间,底层水体处于厌氧状态,底层水体氨氮浓度明显增加;热分层消失后,底层水体溶解氧、总磷及悬浮颗粒物含量均增加.研究表明,对于四季分明的亚热带中等深度的水库而言,水体热分层主要受太阳辐射的控制,稳定的热分层有利于蓝藻门相关种属藻类的生长,热分层形成及消散阶段改变了沉积物的营养盐释放及供给水体的强度,对水体水质形成冲击.在水库水质监控及生态保护管理中,应关注热分层过程的不利影响,并探索相关灾害的防控技术.     

Air pollutant source characterization using the revised regional haze tracking metric and a photochemical grid model and implications for regional haze planning

The 2017 revisions to the Regional Haze Rule clarify that visibility progress at Class I national parks and wilderness areas should be tracked on days with the highest anthropogenic contributions to haze (impairment). We compare the natural and anthropogenic contributions to haze in the western United States in 2011 estimated using the Environmental Protection Agency (EPA) recommended method and using model projections from the Comprehensive Air Quality Model with Extensions (CAMx) and the Particulate Source Apportionment Tool (PSAT). We do so because these two methods will be used by states to demonstrate visibility progress by 2028. If the two methods assume different natural and anthropogenic contributions, the projected benefits of reducing U.S. anthropogenic emissions will differ. The EPA method assumes that episodic elevated carbonaceous aerosols greater than an annual 95th percentile threshold are natural events. For western U.S. IMPROVE monitoring sites reviewed in this paper, CAMx-PSAT confirms these episodes are impacted by carbon from wildfire or prescribed fire events. The EPA method assumes that most of the ammonium sulfate is anthropogenic in origin. At most western sites CAMx-PSAT apportions more of the ammonium sulfate on the most impaired days to global boundary conditions and anthropogenic Canadian, Mexican, and offshore shipping emissions than to U.S. anthropogenic sources. For ammonium nitrate and coarse mass, CAMx-PSAT apportions greater contributions to U.S. anthropogenic sources than the EPA method assigns to total anthropogenic contributions. We conclude that for western IMPROVE sites, the EPA method is effective in selecting days that are likely to be impacted by anthropogenic emissions and that CAMx-PSAT is an effective approach to estimate U.S. source contributions. Improved inventories, particularly international and natural emissions, and further evaluation of global and regional model performance and PSAT attribution methods are recommended to increase confidence in modeled source characterization.

Implications: The western states intend to use the CAMx model to project visibility progress by 2028. Modeled visibility response to changes in U.S. anthropogenic emissions may be less than estimated using the EPA assumptions based on total U.S. and international anthropogenic contributions to visibility impairment. Additional model improvements are needed to better account for contributions to haze from natural and international emissions in current and future modeling years. These improvements will allow more direct comparison of model and EPA estimates of natural and anthropogenic contributions to haze and future visibility progress.     

Composition and element solubility of magnetic and non-magnetic fly ash fractions

Magnetic and non-magnetic fractions of coal fly ashes from SE US electric power plants were characterized with special emphasis on the potential environmental consequences of their terrestrial disposal. Quartz and mullite were the crystalline minerals dominating the non-magnetic fractions. Magnetic fractions contained magnetite, hematite, and, to a lesser extent, quartz and mullite. Chemical analyses revealed that magnetic fractions had about 10 times higher concentrations of Fe, and 2-4 times higher concentrations of Co, Ni, and Mn. Non-magnetic fractions were enriched in K, Al and Ca. Iron content within fly ash particles was negatively correlated with elements associated with aluminosilicate matrix (Si, Al, K, Na). Solubility of most elements was higher in the non-magnetic than in the magnetic fractions of alkaline fly ashes at comparable pH. Calcium was associated with the non-magnetic fraction of the alkaline fly ashes which resulted in a higher pH buffering capacity of this fraction.     

Fire Effects on Carbon and Nitrogen Budgets in Forests

Estimates of C and N loss by gasification during a wildfire in a Jeffrey pine (Pinus Jeffreyii [Grev. and Balf.]) forest in Little Valley, Nevada are compared to potential losses in more mesic forests in the Integrated Forest Study (IFS). In Little Valley, the fire consumed the forest floor, foliage, and an unknown amount of soil organic matter, but little standing large woody material. On an ecosystem level, the fire consumed approximately equal percentages of C and N (12 and 9%, respectively), but a considerably greater proportion of aboveground N (71%) than C (21%). Salvage logging was the major factor in loss, and C lost from the site will not be replenished until forest vegetation is established and succeeds the current shrub vegetation. N₂ fixation by Ceanothus velutinus [Dougl.] in the post-fire shrub vegetation appears to have more than made up for N lost by gasification in the fire over the first 16 yr, and may result in long-term increases in C stocks once forest vegetation takes over the site. N loss from the fire equaled > 1,000 years of atmospheric N deposition and > 10,000 years of N leaching at current rates. Calculations of C and N losses from theoretical wildfires in the IFS sites show similar patterns to those in Little Valley. Calculated losses of N in most of the IFS sites would equal many centuries of leaching. Conceptual models of biogeochemical cycling in forests need to include episodic events such as fire.     

IRRIGATION METHODS AND TRANSPORT OF IMAZAMETHABENZ‐METHYL TO GROUND WATER: GREENFIELDS BENCH,MONTANA1

ABSTRACT: A series of gravel terraces support a shallow aquifer that is the sole source of drinking water for three public water supplies and more than 400 private wells on the Greenfields Bench in west‐central Montana. Farming practices on the Greenfields Bench include irrigation of malting barley and the yearly application of herbicides for the control of weeds. The most commonly used herbicide (imazamethabenz‐methyl, U.S. trade name Assert®) has been found in the ground water on the Greenfields Bench. An experiment was conducted in 2000 and 2001 to characterize the transport of Assert and its acid metabolite to ground water under three irrigation methods: flood, wheel line sprinkler, and center pivot sprinkler. Results show that Assert concentrations in ground water are controlled by hydraulic loading rates of each irrigation method, Assert persistence in soil, hydraulic characteristics of the aquifer, and adsorption/desorption of Assert onto clay particles and organic matter.