Air-Surface Exchange of Mercury with Soils Amended with Ash Materials

Abstract

Air-surface exchange of mercury (Hg) was measured from soil low in Hg (0.013 mg/kg) amended with four different ash materials: a wood ash containing ～10% coal ash (0.070 mg/kg Hg), a mixture of two subbituminous coal fly ashes (0.075 mg/kg Hg), a subbituminous coal ash containing ～10% petroleum coke ash (1.2 mg/kg Hg), and an ash from incinerated municipal sewage sludge (4.3 mg/kg Hg) using a dynamic flux chamber. Ash was added to soil to simulate agricultural supplements, soil stabilization, and pad layers used in livestock areas. For the agricultural amendment, ～0.4% ash was well mixed into the soil. To make the stabilized soil that could be used for construction purposes, ～20% ash was mixed into soil with water. The pad layer consisted of a wetted 1-cm layer of ash material on the soil surface. Diel trends of Hg flux were observed for all of the substrates with significantly higher Hg emissions during the day and negligible flux or deposition of Hg during the night. Hg fluxes, which were measured in the summer months, were best correlated with solar radiation, temperature, and air O₃ concentrations. Mean Hg fluxes measured outdoors for unamended soils ranged from 19 to 140 ng/m² day, whereas those for soil amended with ash to simulate an agricultural application ranged from 7.2 to 230 ng/m² day. Fluxes for soil stabilized with ash ranged from 77 to 530 ng/m² day and for soil with pads constructed of ash ranged from ?50 to 90 ng/m² day. Simple analytical tests (i.e., total Hg content, synthetic precipitation leaching procedure, heating, and indoor gas-exchange experiments) were performed to assess whether algorithms based on these tests could be used to predict Hg fluxes observed outdoors using the flux chamber. Based on this study, no consistent relationships could be developed. More work is needed to assess long-term and seasonal variations in Hg flux from (intact and disturbed) substrates before annual estimates of emissions can be developed.     

Air-surface exchange of mercury with soils amended with ash materials

Air-surface exchange of mercury (Hg) was measured from soil low in Hg (0.013 mg/kg) amended with four different ash materials: a wood ash containing -10% coal ash (0.070 mg/kg Hg), a mixture of two subbituminous coal fly ashes (0.075 mg/kg Hg), a subbituminous coal ash containing -10% petroleum coke ash (1.2 mg/kg Hg), and an ash from incinerated municipal sewage sludge (4.3 mg/kg Hg) using a dynamic flux chamber. Ash was added to soil to simulate agricultural supplements, soil stabilization, and pad layers used in livestock areas. For the agricultural amendment, -0.4% ash was well mixed into the soil. To make the stabilized soil that could be used for construction purposes, -20% ash was mixed into soil with water. The pad layer consisted of a wetted 1-cm layer of ash material on the soil surface. Diel trends of Hg flux were observed for all of the substrates with significantly higher Hg emissions during the day and negligible flux or deposition of Hg during the night. Hg fluxes, which were measured in the summer months, were best correlated with solar radiation, temperature, and air O3 concentrations. Mean Hg fluxes measured outdoors for unamended soils ranged from 19 to 140 ng/m2 day, whereas those for soil amended with ash to simulate an agricultural application ranged from 7.2 to 230 ng/m2 day. Fluxes for soil stabilized with ash ranged from 77 to 530 ng/m2 day and for soil with pads constructed of ash ranged from -50 to 90 ng/m2 day. Simple analytical tests (i.e., total Hg content, synthetic precipitation leaching procedure, heating, and indoor gas-exchange experiments) were performed to assess whether algorithms based on these tests could be used to predict Hg fluxes observed outdoors using the flux chamber. Based on this study, no consistent relationships could be developed. More work is needed to assess long-term and seasonal variations in Hg flux from (intact and disturbed) substrates before annual estimates of emissions can be developed.     

Advances with supercritical fluids

In the last decade, supercritical fluids more and more have been proved as environmentally benign media for chemical and related processes. Many new processes and products have been developed, using the inherent physical and chemical properties of supercritical fluids. Moreover, these processes also promise economic effects. The prerequisites for this success however, are a sound knowledge of physico-chemical properties of--and phenomena in--supercritical mixtures and the availability of other chemical engineering data. This requires an effective exchange of knowledge between a large number of branches of science. In the following, a lot of recent papers will be cited, which should give an overview of actual results on fundamentals and their applications.     

Evolution of clog formation with time in columns permeated with synthetic landfill leachate

Laboratory column tests conducted to gain insight regarding the biological and chemical clogging mechanisms in a porous medium are presented. To seed the porous medium with landfill bacteria, a mixture of Keele Valley Landfill and synthetic leachate permeated through the column under anaerobic conditions for the first 9 days of operation. After this, 100% synthetic leachate was used. The synthetic leachate approximated Keele Valley Landfill leachate in chemical composition but contained negligible suspended solids and bacteria compared with real leachate. The removal of volatile fatty acids (VFAs), primarily acetate, in leachate as it passed through the medium was highly correlated with the precipitation of calcium carbonate (CaCO(3(s))) from solution. The columns experienced a decrease in drainable porosity from an initial value of about 0.38 to less than 0.1 after steady state chemical oxygen demand (COD) removal, resulting in a five-order magnitude decrease in hydraulic conductivity. The decrease in drainable porosity prior to steady state COD removal was primarily due to the growth of a biofilm on the medium surface. After steady state COD removal, calcium precipitation was at least equally responsible for the decrease in drainable porosity as biofilm growth. Clog composition analyses showed that CaCO(3(s)) was the dominant clog constituent and that 99% of the carbonate in the clog material was bound to calcium.     

Rapid treatment of water contamined with atrazine and parathion with zero-valent iron.

The utility of fine-grained iron metal in the remediation of water contamined with Atrazine and Parathion was investigated. Batch procedures under water treatment conditions (ambient temperature and pH of approximately 7) indicated that these pesticides degrade rapidly in the presence of iron powder (40-60 mesh, 40 g/l). The decline in the concentration of pesticide was monitored by HPLC. Experiments with unbuffered solutions showed a steady increase in pH values during the reactions. Therefore, experiments were run in buffered solutions. Different buffered solutions resulted in different degradation rates indicating that the buffer plays an important role in enhancing the degradation process. Tests were also performed on an industrial effluent solution containing a variety of pesticides. Although the products of degradation were not characterized, our HPLC results indicated the disappearance of all the parent pollutants.     

Phytoremediation of pyrene contaminated soils amended with compost and planted with ryegrass and alfalfa

Ryegrass (Lolium perenne) and alfalfa (Medicago sativa) were planted in pots to remediate pyrene contaminated quartz sand (as a control group), alluvial and red soils amended with and without compost. The pyrene degradation percentages in quartz sand, alluvial soil, and red soil amended with compost (5%, w/w) and planted with ryegrass and alfalfa for 90 d growth were 98-99% and 97-99%, respectively, while those of pyrene in the corresponding treatments amended without compost but planted with ryegrass and alfalfa were 91-96% and 58-89%, respectively. Further, those of pyrene in the respective treatments amended with and without compost but unplanted were 54-77% and 51-63%, respectively. Pyrene contents in both roots and aboveground parts of ryegrass and alfalfa after 90 d growth in quartz sand and the two soils amended with or without compost were trace amounts. Statistical analyses for the parameters of ryegrass planted in red and alluvial soils including the concentrations of total water-soluble volatile low molecular weight organic acids, microbial population, pyrene degradation percentage, and spiked pyrene concentration show significant correlations at 5% and mostly 1% probability levels, by the analysis of variance. It was thus suggested that the interactions among the consortia of plant root exudates, microorganisms, and amended compost in rhizosphere soils could facilitate bioavailability of pyrene and subsequently enhance its dissipation.     

Maximum ground-level concentrations with downwash--analysis

Equations derived previously for critical downwind distance xc' wind speed uc' and plume rise zc' the values that produce maximum ground-level concentrations (MGLC) chi c under downwash conditions, have been solved. Tables of chi c' xc' uc' and zc' and graphs of the relationships among uc and zc, for a range of stack heights hs' and building heights hb' are presented. Results for two types of sources--a turbine and a reciprocating engine--are discussed. Some comparisons are made to the U.S. Environmental Protection Agency's (EPA) SCREEN3 model.     

二氧化氯杀灭小球藻

实验研究了二氧化氯投加量、小球藻的初始浓度、pH、有机物和氨氮含量对ClO2杀灭来自于水库水的小球藻的影响,考察了ClO2氧化与混凝工艺结合时去除小球藻的效果并对工艺条件进行优化。结果表明,ClO2在投加量1.1 mg/L下,接触10 min,小球藻的杀灭率为71.93%。小球藻的杀灭率随着ClO2投加量的增大和藻初始浓度的升高而提高,随水中有机物含量的增加而显著降低,氨氮含量对小球藻杀灭的效果影响很小。在酸性条件和碱性条件下,小球藻的杀灭率均随pH升高而急剧下降,而在中性至弱碱性区间内,藻的杀灭率随pH升高而缓慢下降。对于某以小球藻为优势藻的供水水库源水,ClO2氧化与混凝工艺结合,藻的去除率高达98.47%。除藻的最佳工艺条件为：二氧化氯投加量为0.5 mg/L,聚合氯化铝为5 mg/L,二氧化氯与混凝剂同时投加。     

Urban emissions measured with aircraft

Detailed knowledge of the quantity and composition of urban emissions is a prerequisite for successful application of atmospheric models to predict transport and distribution of primary and secondary air pollutants in the troposphere. We investigate the prospects and limitations of aircraft measurements in the determination of emission fluxes from urban areas. Our analysis focuses on data collected in September 1994 in and around Athens, Greece. Generally, emission fluxes from cities can be quantified with aircraft and with the minimum acceptable precision (uncertainty better than a factor of 2) only under very favorable meteorological conditions, namely in a homogeneous flow field in a well-mixed boundary layer. Better accuracy can be achieved only through ensemble averaging of repeated measurements. From our measurements in the Athens area, we deduced relative emission ratios of pollutant gases. With the support of ground-based measurements in a street canyon, the emission ratios NOx/CO, SO2/CO, and volatile organic compounds/CO (34 individual VOCs) could be determined with high precision. These results are very useful in analyzing differences between various existing emission inventories. Our data for VOCs reveal that the non-traffic emissions are of the same magnitude as the emissions originating from traffic.     

Maximum Ground-Level Concentrations with Downwash

Equations are derived from the Gaussian plume mode! and prescribe the critical downwind distance, wind speed, and plume rise values that result in maximum ground-level concentrations (MGLC) under downwash conditions. The derivations apply to bent-over plumes and encompass the Schulman-Scire and Huber-Snyder building downwash treatments.     

Interactions of uranium with polyphosphate

Inorganic polyphosphates (PolyP) are simple linear phosphate (PO(4)(3-)) polymers which are produced by a variety of microorganisms. One of their functions is to complex metals resulting in their precipitation. We investigated the interaction of phosphate and low-molecular-weight PolyP (1400-1900Da) with uranyl ion at various pHs. Potentiometric titration of uranyl ion in the presence of phosphate showed two sharp inflection points at pHs 4 and 8 due to uranium hydrolysis reaction and interaction with phosphate. Titration of uranyl ion and PolyP revealed a broad inflection point starting at pH 4 indicating that complexation of U-PolyP occurs over a wide range of pHs with no uranium hydrolysis. EXAFS analysis of the U-HPO(4) complex revealed that an insoluble uranyl phosphate species was formed below pH 6; at higher pH (> or = 8) uranium formed a precipitate consisting of hydroxophosphato species. In contrast, adding uranyl ion to PolyP resulted in formation of U-PolyP complex over the entire pH range studied. At low pH (< or = 6) an insoluble U-PolyP complex having a monodentate coordination of phosphate with uranium was observed. Above pH 6 however, a soluble bidentate complex with phosphate and uranium was predominant. These results show that the complexation and solubility of uranium with PO(4) and PolyP are dependent upon pH.     

Testing biodegradability with standardized methods

Laboratory test methods are used by industry laboratories to determine biodegradability, an important parameter for the evaluation of the ecological behaviour of substances. Biodegradability has a key role due to the simple fact that a degradable substance will cause no long term risk in the environment. The great variety of biodegradation processes in the natural environment and in technical plants for treating waste water and solid wastes gave rise to a rather large number of test methods based on different test principles. To guarantee the acceptance of the test results by authorities and customers internationally standardized methods (ISO, OECD) and established quality criteria (GLP, EN 45000, ISO 9000) are used.     

Unsolved Problems with Flue-FED Incinerators

At the beginning of the federal program in 1955, air pollution was viewed as a technical challenge. While technical problems remain, emphasis is shifting toward the social challenge. The degree of federal assistance now available to states and municipalities, under the Clean Air Act, is of broadened scope and higher order of magnitude; it is not confined to technical considerations, but has been expanded to take cognizance of political and economic obstacles that often block the path toward better air pollution control.     

The reaction of nitrogen dioxide with lung surface components: The reaction with cholesterol

The reaction of nitrogen dioxide (NO₂) with cholesterol was investigated. NO₂ reacted with the hydroxyl group in cholesterol to produce cholesteryl nitrite. In this reaction, other minor products were observed. Cholesteryl nitrate, however, was not detected as was reported by other workers. Water accelerates and oxygen retards this reaction.     

Microbial growth with vapor-phase substrate

Limited information exists on influences of the diffusive transport of volatile organic contaminants (VOC) on bacterial activity in the unsaturated zone of the terrestrial subsurface. Diffusion of VOC in the vapor-phase is much more efficient than in water and results in effective VOC transport and high bioavailability despite restricted mobility of bacteria in the vadose zone. Since many bacteria tend to accumulate at solid-water, solid-air and air-water interfaces, such phase boundaries are of a special interest for VOC-biodegradation. In an attempt to evaluate microbial activity toward air-borne substrates, this study investigated the spatio-temporal interplay between growth of Pseudomonas putida (NAH7) on vapor-phase naphthalene (NAPH) and its repercussion on vapor-phase NAPH concentrations. Our data demonstrate that growth rates of strain PpG7 were inversely correlated to the distance from the source of vapor-phase NAPH. Despite the high gas phase diffusivity of NAPH, microbial growth was absent at distances above 5 cm from the source when sufficient biomass was located in between. This indicates a high efficiency of suspended bacteria to acquire vapor-phase compounds and influence headspace concentration gradients at the centimeter-scale. It further suggests a crucial role of microorganisms as biofilters for gas-phase VOC emanating from contaminated groundwater or soil.     

Denitrification with carbon addition--kinetic considerations

The Blue Plains Advanced Wastewater Treatment Plant (Washington, D.C.) uses methanol as an external carbon source in a postdenitrification process, to achieve low effluent total nitrogen concentrations. This becomes more difficult in winter, at lower mixed liquor temperatures and higher flows, as a consequence of the kinetic behavior of the methanol-utilizing heterotrophs. The paper reports on an experimental batch test study conducted on Blue Plains postdenitrification sludge to investigate (1) the maximum specific growth rate of methanol-utilizing heterotrophs (Mu(METH)); (2) the temperature dependency of the growth rate; and (3) the efficacy of alternate substrates (ethanol, acetate, and sugar). A limited number of tests were conducted on sludge from two other treatment plants with methanol addition.     

Living with floating vegetation invasions

Invasions of water bodies by floating vegetation, including water hyacinth (Eichhornia crassipes), are a huge global problem for fisheries, hydropower generation, and transportation. We analyzed floating plant coverage on 20 reservoirs across the world’s tropics and subtropics, using > 30 year time-series of LANDSAT remote-sensing imagery. Despite decades of costly weed control, floating invasion severity is increasing. Floating plant coverage correlates with expanding urban land cover in catchments, implicating urban nutrient sources as plausible drivers. Floating vegetation invasions have undeniable societal costs, but also provide benefits. Water hyacinths efficiently absorb nutrients from eutrophic waters, mitigating nutrient pollution problems. When washed up on shores, plants may become compost, increasing soil fertility. The biomass is increasingly used as a renewable biofuel. We propose a more nuanced perspective on these invasions moving away from futile eradication attempts towards an ecosystem management strategy that minimizes negative impacts while integrating potential social and environmental benefits.Electronic supplementary materialThe online version of this article (10.1007/s13280-020-01360-6) contains supplementary material, which is available to authorized users.     

Positive ion clustering with acetonitrile

In order to study ion clustering in air mixed with CH₃CN, laboratory experiments were performed using an ion source coupled to a mass spectrometer. The study of the positive ions H⁺(CH₃CN)_m (H₂O)_n and the determination of their equilibrium constants lead to a better understanding of cluster formation processes with atmospheric trace gases.