A reaction-transport model for calcite precipitation and evaluation of infiltration fluxes in unsaturated fractured rock

The percolation flux in the unsaturated zone (UZ) is an important parameter addressed in site characterization and flow and transport modeling of the potential nuclear-waste repository at Yucca Mountain, NV, USA. The US Geological Survey (USGS) has documented hydrogenic calcite abundances in fractures and lithophysal cavities at Yucca Mountain to provide constraints on percolation fluxes in the UZ. The purpose of this study was to investigate the relationship between percolation flux and measured calcite abundances using reactive transport modeling. Our model considers the following essential factors affecting calcite precipitation: (1) infiltration, (2) the ambient geothermal gradient, (3) gaseous CO(2) diffusive transport and partitioning in liquid and gas phases, (4) fracture-matrix interaction for water flow and chemical constituents, and (5) water-rock interaction. Over a bounding range of 2-20 mm/year infiltration rate, the simulated calcite distributions capture the trend in calcite abundances measured in a deep borehole (WT-24) by the USGS. The calcite is found predominantly in fractures in the welded tuffs, which is also captured by the model simulations. Simulations showed that from about 2 to 6 mm/year, the amount of calcite precipitated in the welded Topopah Spring tuff is sensitive to the infiltration rate. This dependence decreases at higher infiltration rates owing to a modification of the geothermal gradient from the increased percolation flux. The model also confirms the conceptual model for higher percolation fluxes in the fractures compared to the matrix in the welded units, and the significant contribution of Ca from water-rock interaction. This study indicates that reactive transport modeling of calcite deposition can yield important constraints on the unsaturated zone infiltration-percolation flux and provide useful insight into processes such as fracture-matrix interaction as well as conditions and parameters controlling calcite deposition.     

Gender and career success: A typology and analysis of dual paradigms

Despite women's advancements in the workplace, gender inequality persists. We classify and test two frameworks used to explain gender differences in career success: unequal attributes and unequal effects. The unequal attributes framework suggests that gender is related to other attributes, which result in unequal career outcomes for men and women (i.e., a mediated effect). The unequal effects framework suggests that even when men and women share the same attribute or circumstances, they are rewarded differently, such that individual attributes have unequal effects on career outcomes for men and women (i.e., a moderated effect). We collected survey data from a gender‐balanced sample of 394 business school alumni. Using structural equation modeling to test the unequal attributes framework, we found that work hours, career orientation, having a nonemployed spouse, and working in a predominantly female job were unequal attributes that explained gender differences in career success. Using multigroup path analysis to examine unequal effects, we found that being agentic, married, having children at home, and working in a predominantly female workplace had unequal effects in relation to career success for men and women. We find support for both models across three categories of career success antecedents (i.e., personal, family, and job attributes).     

Conceptual and numerical model of uranium(VI) reductive immobilization in fractured subsurface sediments

A conceptual model and numerical simulations of bacterial U(VI) reduction in fractured subsurface sediments were developed to assess the potential feasibility of biomineralization at the fracture/matrix interface as a mechanism for immobilization of uranium in structured subsurface media. The model envisions flow of anaerobic groundwater, with or without acetate as an electron donor for stimulation of U(VI) reduction by dissimilatory metal-reducing bacteria (DMRB), within mobile macropores along a one-dimensional flow path. As the groundwater moves along the flow path, U(VI) trapped in the immobile mesopore and micropore domains (the sediment matrix) becomes desorbed and transferred to the mobile macropores (fractures) via a first-order exchange mechanism. By allowing bacterial U(VI) reduction to occur in the mesopore domain (assumed to account for 12% of total sediment pore volume) according to experimentally-determined kinetic parameters and an assumed DMRB abundance of 10(7) cells per cm3 bulk sediment (equivalent to 4 mg of cells per dm3 bulk sediment), the concentration of U(VI) in the macropore domain was reduced ca. 10-fold compared to that predicted in the absence of mesopore DMRB activity after a 6-month simulation period. The results suggest that input of soluble electron donors over a period of years could lead to a major redistribution of uranium in fractured subsurface sediments, converting potentially mobile sorbed U(VI) to an insoluble reduced phase (i.e. uraninite) in the mesopore domain that is expected to be permanently immobile under sustained anaerobic conditions.     

Interactive analysis of waste recycling and energy recovery program in a small-scale incinerator

Conflicting goals affecting solid waste management are explored in this paper to find the best implementation of resource recovery with a small-scale waste-to-energy process. Recycling paper and plastic material often leaves a shortage of thermal energy to support incineration that forces operators to supplement the process with auxiliary fuels. Although there are considerable profits to be made from material recovery, the increase of fuel usage causes conflict given that it is cost prohibitive. A series of trials performed on a small-scale 1.5-t/day incineration plant with a cyclone heat recovery system found that material recycling can impede performance. Experimental results are expressed as empirical regression formulas with regard to combustion temperature, energy transfer, and heat recovery. Process optimization is possible if the waste moisture content remains <30%. To test the robustness of the optimization analysis, a series of sensitivity analyses clarify the extent of material recycling needed with regard to plastic, paper, and metal. The experiments also test whether the moisture in the waste would decrease when recycling paper because of its exceptional capacity to absorb moisture. Results show that recycling paper is strongly recommended when the moisture content is >20%, whereas plastic recycling is not necessary at that moisture condition. Notably, plastic recovery reduces the heat needed to vaporize the water content of the solid waste, thus it is recommended only when the moisture content is <10%. For above-normal incineration temperatures, plastic recycling is encouraged, because it removes excess energy. Metal is confirmed as an overall priority in material recycling regardless of the moisture content of the incoming waste.     

Simultaneous conversion of CHClF(2) and CH(3)Br to CH(2)CF(2)

Gas phase reaction of CHClF(2) with CH(3)Br in an alumina tube reactor at 773-1123 K as a function of various input ratios of CH(3)Br to CHClF(2) is presented. The major products detected include C(2)F(4), CH(2)CF(2), and CH(4). Minor products include CH(3)Cl, CHF(3), C(2)H(4), C(2)H(2), CH(2)CF-CF(3), and C(2)H(3)F. The reaction produces a high yield of CH(2)CF(2) (53% based on CHClF(2) feed) at 1123 K and an input molar ratio of CH(3)Br to CHClF(2) of 1.8, suggesting that the reaction potentially can be developed as a process to convert two ozone depleting substances (CHClF(2) and CH(3)Br) to a highly valuable chemical, CH(2)CF(2). The reaction of CHClF(2) with CH(3)Cl and CH(3)I was also investigated under similar reaction conditions, to assist in understanding the reaction chemistry involved in the reaction of CHClF(2) with CH(3)Br.     

Refinery evaluation of optical imaging to locate fugitive emissions

Fugitive emissions account for approximately 50% of total hydrocarbon emissions from process plants. Federal and state regulations aiming at controlling these emissions require refineries and petrochemical plants in the United States to implement a Leak Detection and Repair Program (LDAR). The current regulatory work practice, U.S. Environment Protection Agency Method 21, requires designated components to be monitored individually at regular intervals. The annual costs of these LDAR programs in a typical refinery can exceed US$1,000,000. Previous studies have shown that a majority of controllable fugitive emissions come from a very small fraction of components. The Smart LDAR program aims to find cost-effective methods to monitor and reduce emissions from these large leakers. Optical gas imaging has been identified as one such technology that can help achieve this objective. This paper discusses a refinery evaluation of an instrument based on backscatter absorption gas imaging technology. This portable camera allows an operator to scan components more quickly and image gas leaks in real time. During the evaluation, the instrument was able to identify leaking components that were the source of 97% of the total mass emissions from leaks detected. More than 27,000 components were monitored. This was achieved in far less time than it would have taken using Method 21. In addition, the instrument was able to find leaks from components that are not required to be monitored by the current LDAR regulations. The technology principles and the parameters that affect instrument performance are also discussed in the paper.     

Synergistic vulnerabilities: climate variability and fire management policy increase farming challenges in southeastern Mexico

Agricultural fire for land preparation is central in the livelihoods of subsistence farmers practicing shifting cultivation. Achieving a good agricultural burn, one in which the biomass is thoroughly consumed within the chosen area, depends on specific weather conditions. Fire use decisions are also shaped by institutions that define the timing and rules for fire use but also constrain the alternatives and shape adaptive capacities. Global and regional climate changes interact with the institutional framing of fire management affecting local fire use and burn outcomes. These effects are documented and analyzed to suggest adaptations to existing governance systems. We examined subsistence farmers’ socio-ecological vulnerability in the Calakmul municipality, located in southeastern Mexico. Using interviews with farmers and government agents, as well as participatory mapping and observation of agricultural burns, we studied fire management knowledge, practices and burn outcomes. Our results describe a continuum of burn outcomes covering good agricultural burns, uncontrolled burns leading to wildfires and “malquemados” literally poorly burned areas. Malquemados represent unsuccessful combustion associated with excess moisture that results in scorched vegetation. We discuss how unexpected early rains trigger effects that cascade through space and the ecological, economic and cultural domains. We argue that fire management has been historically approached from a conservation standpoint yet agricultural fire use and wildfire prevention should also be addressed from a rural development perspective. This shift in fire management would lead to the proper inclusion of the entire array of burn outcomes in studies and policies addressing farmers’ vulnerability amplified by synergistic effects between climate variability and institutional change.     

Awareness of environmental legislation as a deterrent for wildlife crime: A case with Masaai pastoralists,poison use and the Kenya Wildlife Act

Illegal wildlife crime is a global phenomenon, accelerating the ongoing biodiversity crisis. In the Old World, and particularly in Africa, illegal use of poisons to eliminate carnivores is the main driver of the continental vulture crisis. Knowledge about the underlying source and drivers of this threat is lacking for most areas, including Kenya, a global vulture and biodiversity hotspot. An extensive questionnaire survey of over 1300 respondents was run, using a specialized questioning technique and quantitative analytical approaches. Results show that, while pastoralists have a positive attitude towards vultures, over 20% of them use poisons to eliminate predators. Poisoning was largely driven by livestock losses to predators, and by negative attitude towards predators. Poisoning was less prevalent among respondents aware of the Kenya Wildlife Act. Overall, we suggest that a combination of top-down, e.g. legislation, and bottom-up (such as corrals or compensation) along with awareness campaigns may help reduce poisoning on the ground.Supplementary InformationThe online version contains supplementary material available at 10.1007/s13280-021-01695-8.     

First assessment of persistent organic pollutants in the Greater rhea (Rhea americana), a near-threatened flightless herbivorous bird of the Pampas grasslands

Environmental Science and Pollution Research - Persistent organic pollutants (POPs) are still globally distributed and can exert different effects on ecosystems. Little is known about the...     

Heavy metal mobility in runoff water and absorption by eggplant fruits from sludge treated soil

Sewage sludge addition to agricultural lands requires judicious management to avoid environmental risks arising from heavy metal and nitrate contamination of surface water and accumulation in edible plants. A field study was conducted on a silty-loam soil of 10% slope at Kentucky State University Research Farm. Eighteen plots of 22 x 3.7 m each were separated using metal borders and the soil in six plots was mixed with sewage sludge and yard waste compost mix (SS-YW) at 15 t acre(-1), six plots were mixed with sewage sludge (SS) at 15 t acre(-1), and six unamended plots that never received sludge were used for comparison purposes. Plots were planted with eggplant, Solanum melongena L. as the test plant. The objectives of this investigation were to: 1) assess the effect of soil amendments on the transport of NO3, NH4, and heavy metals (Cd, Cr, Ni, Pb, Zn, Cu, and Mo) into surface water; 2) investigate the effect of soil amendments on heavy metal bioavailability in eggplant fruits at harvest; and 3) assess chemical and physical properties of soil following addition of soil amendments and their impact on the yield and quality of eggplant fruit. SS-YW treatments reduced runoff water by 63% while plots incorporated with sewage sludge alone reduced runoff water by 37% compared to control treatment. The SS-YW treatments transported more mineral nitrogen (NO3-N and NH4-N) in runoff water than SS treatments. Total marketable yield (lbs acre(-1)) and number of eggplant fruits were greatest in SS-YW treatments. This response may be due to improved soil porosity, water, and nutrient retention of the soil amended with SS-YW mixture. Concentrations of heavy metals in soil amended with sludge were below the U.S. Environmental Protection Agency (USEPA) limits. Chromium, Ni, Zn, and Cu were taken up by eggplant fruits but their concentrations were below the Codex Commission allowable levels.