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Tracing the incorporation of carbon into benthic foraminiferal calcite following the Deepwater Horizon event
2018
Schwing, Patrick T. | Chanton, Jeffrey P. | Romero, Isabel C. | Hollander, David J. | Goddard, Ethan A. | Brooks, Gregg R. | Larson, Rebekka A.
Following the Deepwater Horizon (DWH) event in 2010, hydrocarbons were deposited on the continental slope in the northeastern Gulf of Mexico through marine oil snow sedimentation and flocculent accumulation (MOSSFA). The objective of this study was to test the hypothesis that benthic foraminiferal δ13C would record this depositional event. From December 2010 to August 2014, a time-series of sediment cores was collected at two impacted sites and one control site in the northeastern Gulf of Mexico. Short-lived radioisotopes (210Pb and 234Th) were employed to establish the pre-DWH, DWH, and post-DWH intervals. Benthic foraminifera (Cibicidoides spp. and Uvigerina spp.) were isolated from these intervals for δ13C measurement. A modest (0.2–0.4‰), but persistent δ13C depletion in the DWH intervals of impacted sites was observed over a two-year period. This difference was significantly beyond the pre-DWH (background) variability and demonstrated that benthic foraminiferal calcite recorded the depositional event. The longevity of the depletion in the δ13C record suggested that benthic foraminifera may have recorded the change in organic matter caused by MOSSFA from 2010 to 2012. These findings have implications for assessing the subsurface spatial distribution of the DWH MOSSFA event.
Show more [+] Less [-]Evaluation of the ability of calcite, bentonite and barite to enhance oil dispersion under arctic conditions
2018
A test program was conducted at laboratory and pilot scale to assess the ability of clays used in drilling mud (calcite, bentonite and barite) to create oil-mineral aggregates and disperse crude oil under arctic conditions. Laboratory tests were performed in order to determine the most efficient conditions (type of clay, MOR (Mineral/Oil Ratio), mixing energy) for OMA (Oil Mineral Aggregate) formation. The dispersion rates of four crude oils were assessed at two salinities. Dispersion was characterized in terms of oil concentration in the water column and median OMA size. Calcite appeared to be the best candidate at a MOR of 2:5. High mixing energy was required to initiate OMA formation and low energy was then necessary to prevent the OMAs from resurfacing. Oil dispersion using Corexit 9500 was compared with oil dispersion using mineral fines.
Show more [+] Less [-]Characterization and Leachability Propensity of Bottom Ash from Medical Waste Incineration
2018
Allawzi, Mamdouh | Al-harahsheh, Mohammad | Allaboun, Hussein
The leachability of bottom medical waste ash from a Jordanian incinerator was studied in this work. The ash was characterized in terms of particle size distribution, chemical and mineralogical composition followed by leaching of several size fractions at different conditions (leaching time, temperature, initial pH, particle size, and solid liquid ratio). The major elements found in the ash were Ca, Si, Al, Cl, Na, Fe, Ti, S, Mg, Ba, and K, while the main mineral phases found in the ash were calcite, halite, sylvite, anhydrite, hematite, hydrochlorborite, cristobalite, melanterite, and chlormayenite. Leaching data indicates that as leaching time and S/L increased, the concentration of metals increased in the leachate. The highest leaching level was at a S/L ratio of 60 mg/ml. As the particles sizes decreased, the concentration of the majority of metals studied increased. Meanwhile, the effect of particle size on other metals was not regular due to the fact that sieving resulted in more concentrated metals in certain particle size fractions. Leachability results also indicate that variation in the initial pH has a slight effect on the degree of leaching. The concentration of some metal ions increased with temperature, while others increased initially but subsequently decreased. The extracted quantities of all the heavy metals were less than the limits set by EPA.
Show more [+] Less [-]Immobilization of Boron and Arsenic in Alkaline Coal Fly Ash through an Aging Process with Water and Elucidation of the Immobilization Mechanism
2018
Ogawa, Yasumasa | Sakakibara, Kento | Seki, Tsugumi | Inoue, Chihiro
We previously reported that a simple treatment—addition of only small amounts of water to coal fly ash (CFA) to form CFA paste followed by aging for 1–4 weeks—is advantageous for the immobilization of highly soluble B, F, Cr, and As. In this study, we investigated the leachability of Ca, SO₄, B, and As over time from non-aged and aged CFA samples to elucidate a possible immobilization mechanism. For this purpose, two types of CFA samples, one showing effective immobilization of B and As by water addition and aging (sample A) and the other showing less or no immobilization (sample B), were examined. Calcium and SO₄, B, and As in non-aged sample A dissolved immediately after the start of the leaching test, indicating that these elements existed in highly soluble particles. After the rapid dissolution, their concentrations in the leachate gradually increased, possibly due to the dissolution of glassy phases. During the 1-week leaching test, the B and As concentrations in the leachate finally decreased. The addition of only small amounts of water to CFA (Sample A) for aging produce both alkaline and supersaturation conditions for the formation of several types of Ca-bearing secondary minerals such as calcite and ettringite, which are formed under alkaline conditions. Boron and As originally existing as highly soluble particles in CFA are expected to be incorporated into and/or sorbed on these secondary minerals as water-insoluble phases. Compared to non-aged CFA, their leachability from the aged sample A remained lower throughout the entire leaching test. Possibly due to these secondary minerals being formed on the CFA surface, B and As dissolutions associated with glassy phases are also prevented. In contrast, the pH of the leachate from CFA (sample B) at the beginning of the leaching test was acidic and then abruptly became alkaline. This means that water-soluble particles that can produce acidic conditions are also contained in these alkaline CFAs. Dissolution of these substances during aging makes it difficult to generate alkaline conditions in the CFA paste. Consequently, the formation of secondary minerals and the concomitant immobilization of toxic elements are prevented.
Show more [+] Less [-]Long-term trends in Swiss rivers sampled continuously over 39 years reflect changes in geochemical processes and pollution
2018
Zobrist, Juerg | Schoenenberger, Ursula | Figura, Simon | Hug, Stephan J.
Long-term changes of 14 water constituents measured in continuously and water discharge proportionally collected samples of four Swiss rivers over a period of 39 years are analyzed using several statistical techniques. Possible drivers and causes for the identified trends and shifts are explained by consideration of catchment characteristics and anthropogenic activities. Water temperatures increased by 0.8–1.3 °C, whereas water discharges remained largely unchanged. Concentrations of alkalinity, total hardness, Ca, and Mg regulated by dominant carbonate lithologies in catchments increased by up to 10%. We attribute this change to an increase in the partial pressure of CO₂ in the subsurface, provoked by increasing temperatures. Re-oligotrophication processes in lakes also influence the behavior of alkalinity and silicic acid. In contrast to concentrations, most loads did not change significantly, due to their large variances. Therefore, no changes in overall weathering rates of carbonate rocks can be detected. The outgassing of CO₂ in rivers from the place of carbonate dissolution to measurement stations amounts up to 6% (mean) of CO₂ sequestered (mean 1.1 mol m⁻² a⁻¹) by the weathering of rock minerals. Changes in alkalinity/Ca/Mg ratios indicate an increase in calcite precipitation over time. Total nitrogen concentrations and loads peaked at the end of the 1980s and then decreased up to 50%, while NO₃ concentrations showed almost no changes. This dynamic matches the changes in the agricultural N balance. Concentrations and loads of Na and Cl increased up to 60% due to an increase in the various uses of rock salt.
Show more [+] Less [-]Morphology, molecular structure, and stable carbon isotopic composition of black carbon (BC) in urban topsoils
2018
Zong, Yutong | Xiao, Qing | Lu, Shenggao
Urban soils contain significant amounts of black carbon (BC) from biomass and fossil fuel combustion and regard to be a pool of BC. BC in urban soils has multiple effects on environmental processes in urban system, such as global climate change, air quality, and public health. Urban topsoil samples (0–10 cm) were collected from Anshan, Liaoning Province, northeast China, which is one of the most important old steel industrial bases in China. The BC in urban topsoils was extracted using the density method. Their chemical composition, morphology, molecular structure, and stable carbon isotopic composition were examined using elemental analysis, scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDS), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), X-ray diffraction (XRD), and stable carbon isotope (δ¹³C). Elemental analysis shows that carbon content in the BC of studied soils ranged from 64.5 to 78.4%, with the average more than 70%. The O/C atomic ratio of BC is on average 0.18. The BC particle displays different morphology, including porous spherical, irregular porous fragmentary, and blocky shapes. The porous spherical BC particles has atomic molar O/C ratio determined by SEM-EDS ranging from 0.04 to 0.37. XRD indicates that BC exists in mainly combining with mineral phases hematite (Fe₂O₃), kaolinite (Al₂Si₂O₅(OH)₄), quartz (SiO₂), and calcite (CaCO₃). The FTIR spectra of BC particles show major bands at approximately 3400 cm⁻¹ (O–H), 2920 cm⁻¹ (C = H), 1600 cm⁻¹ (C = C), 1230 cm⁻¹ (C = O), and 1070 cm⁻¹ (C = O). The stable carbon isotope (δ¹³C) of BC ranges from −24.48 to −23.18‰ with the average of −23.79 ± 0.39‰. The concentration of BC in the industrial area is significantly (p < 0.05) higher than that in the roadside area. The BC of industrial area is characterized by porous spherical structure, suggesting that they are mainly derived from fossil fuel combustion. Results indicated that a combination of atomic O/C ratio, porous structure, and stable carbon isotopic (δ¹³C) of BC could reflect effectively the origin of BC in urban topsoils. It could conclude that BC in Anshan urban topsoil was mainly from fossil fuel combustion.
Show more [+] Less [-]Improved strength and durability of concrete through metabolic activity of ureolytic bacteria
2018
Alonso, Maria Jose Castro | Ortiz, Carlos Eloir Lopez | Perez, Sixto Omar Garcia | Narayanasamy, Rajeswari | Fajardo San Miguel, Gerardo del Jesús | Hernández, Héctor Herrera | Balagurusamy, Nagamany
In recent years, biomineralization process is being employed in development of bioconcrete, which is emerging as a sustainable method to enhance the durability of concrete by way of increasing compressive strength and reducing the chloride permeability. In this study, different bacterial strains isolated from the soils of the Laguna Region of Mexico were selected for further study. ACRN5 strain demonstrated higher urease activity than other strains, and the optimum substrate concentration, pH, and temperature were 120 mM, pH 8, and 25 °C, respectively. Further, Km and Vmax of urease activity of ACRN5 were 21.38 mM and 0.212 mM min⁻¹, respectively. It was observed that addition of ACRN5 at 10⁵ cells ml⁻¹ to cement-water mixture significantly increased (14.94%) in compressive strength after 36 days of curing and reduced chloride penetration. Deposition of calcite in bio-mortars was observed in scanning electron microscopy and energy dispersive X-ray diffraction spectrometry analyses. Results of this study demonstrated the role of microbially induced calcium carbonate precipitation in improving the physico-mechanical properties of bio-mortars.
Show more [+] Less [-]Sequential extraction of chromium, molybdenum, and vanadium in basic oxygen furnace slags
2018
Spanka, Marina | Mansfeldt, Tim | Bialucha, Ruth
Basic oxygen furnace slags (BOS) are by-products of basic oxygen steel production. Whereas the solubility of some elements from these slags has been well investigated, information about the mineralogy and related leaching, i.e., availability of the environmentally relevant elements chromium (Cr), molybdenum (Mo), and vanadium (V), is still lacking. The aim of this study was to investigate these issues with a modified, four-fraction-based, sequential extraction procedure (F1–F4), combined with X-ray diffraction, of two BOS. Extractants with increasing strength were used (F1 demineralized water, F2 CH₃COOH + HCl, F3 Na₂EDTA + NH₂OH·HCl, and F4 HF + HNO₃ + H₂O₂), and after each fraction, X-ray diffraction was performed. The recovery of Cr was moderate (66.5%) for one BOS, but significantly better (100.2%) for the other one. High recoveries were achieved for the other elements (Mo, 100.8–107.9% and V, 112.6–87.0%), indicating that the sequential extraction procedure was reliable when adapted to BOS. The results showed that Cr and Mo primarily occurred in F4, representing rather immobile elements under natural conditions, which were strongly bound into/onto Fe minerals (srebrodolskite, magnetite, hematite, or wustite). In contrast, V was more mobile with proportional higher findings in F2 and F3, and the X-ray diffraction results reveal that V was not solely bound into Ca minerals (larnite, hatrurite, kirschsteinite, and calcite), but also bound to Fe minerals. The results indicated that the total amount of recovery was a poor indicator of the availability of elements and did not correspond to the leaching of elements from BOS.
Show more [+] Less [-]Characterization of drilling waste from shale gas exploration in Central and Eastern Poland
2018
Mikos-Szymańska, Marzena | Rusek, Piotr | Borowik, Krzysztof | Rolewicz, Maciej | Bogusz, Paulina | Gluzińska, Joanna
The purpose of this research was to determine and evaluate the chemical properties of drilling waste from five well sites in Central and Eastern Poland. It was found that spent drilling fluids can contain high values of nickel and mercury (270 and 8.77 mg kg⁻¹, respectively) and can exceed the maximum permissible limits recommended by the EC regulations for safety of soils (75 mg kg⁻¹ for nickel and 1.5 mg kg⁻¹ for mercury). The heavy metal concentrations in the studied drill cuttings did not exceed the maximum permissible limits recommended by the EC regulation. Drilling wastes contain macroelements (e.g., calcium, magnesium, and potassium) as well as trace elements (e.g., copper, iron, zinc, and manganese) that are essential for the plant growth. It was stated that water extracts of drilling fluids and drill cuttings, according to anions presence, had not any specific constituents of concern based on FAO irrigation guidelines, the USEPA WQC, and toxicity values. X-ray diffraction analysis was used to understand the structure and texture of waste drilling fluid solids and drill cuttings. Analysis of the mineralogical character of drilling fluid solids revealed that they contained calcite, quartz, muscovite, sylvite, barite, dolomite, and orthoclase. Drill cuttings contained calcite quartz, muscovite, barite, dolomite, and barium chloride.
Show more [+] Less [-]The potential for constructed wetland mechanisms to treat alkaline bauxite residue leachate: carbonation and precipitate characterisation
2018
Higgins, Derek | Curtin, Teresa | Burke, Ian | Courtney, Ronan
Leachates emanating from bauxite residue disposal areas are alkaline and require neutralisation prior to discharge. The use of passive technologies such as constructed wetlands has received increasing interest as possible treatments for alkaline leachates, including bauxite residues. Mechanisms proposed for wetland effectiveness have included calcite precipitation but it is not clear if such a pathway is feasible in the relatively low Ca residue leachates. Carbonation of Ca-spiked residue leachate treatments was conducted to observe rates of pH decrease and precipitate formation. For all treatments, carbonation effectively decreased pH to ca. 10.5 which remained stable following aeration. Decreases in Al content of 83–93% were also observed. Precipitates retrieved from carbonation experiments and from a constructed wetland trial were characterised using XRD, SEM, XPS and EDX. Calcium carbonates formed in Ca-spiked treatments and dawsonite precipitation occur in the absence of Ca. Rinsing of precipitates removes surface calcium indicating soluble forms adsorbed on precipitates. The results demonstrate that carbonation of bauxite residue leachate is an important component of passive treatments and neutralisation.
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