Sample Size Effects on Petrophysical Characterization and Fluid-to-Pore Accessibility of Natural Rocks.

Laboratory-scale analysis of natural rocks provides petrophysical properties such as density, porosity, pore diameter/pore-throat diameter distribution, and fluid accessibility, in addition to the size and shape of framework grains and their contact relationship with the rock matrix. Different types of laboratory approaches for petrophysical characterization involve the use of a range of sample sizes. While the sample sizes selected should aim to be representative of the rock body, there are inherent limitations imposed by the analytical principles and holding capacities of the different experimental apparatuses, with many instruments only able to accept samples at the µm-mm scale. Therefore, a total of nine (three limestones, three shales, two sandstones, and one dolomite) samples were collected from Texas to fill the knowledge gap of the sample size effect on the resultant petrophysical characteristics. The sample sizes ranged from 3 cm cubes to <75 µm particles. Using a combination of petrographic microscopy, helium expansion pycnometry, water immersion porosimetry, mercury intrusion porosimetry, and (ultra-) small-angle X-ray scattering, the impact of sample size on the petrophysical properties of these samples was systematically investigated here. The results suggest that the sample size effect is influenced by both pore structure changes during crushing and sample size-dependent fluid-to-pore connectivity.

Dissolution of Mn-bearing dolomite drives elevated Cr(VI) occurrence in a Permian redbed aquifer.

Municipalities in central Oklahoma, U.S.A. increasingly rely on water drawn from the Central Oklahoma Aquifer (COA) as surface water resources have not grown in proportion to population and current water demands. However, water drawn from certain regions of the COA frequently contains elevated levels of naturally occurring hexavalent chromium. Rock samples from the Norman Arsenic Test Hole Core (NATHC) were investigated to identify the mineralogic host(s) of Cr and mechanisms of Cr(VI) release via bulk mineralogy and chemistry measurements, selective chemical extractions, and microscale elemental analyses. Results demonstrate most COA Cr is contained in Fe oxides and clays as isomorphic substitutions for Fe(III). Analyses of regional groundwater data, including hierarchical clustering methods and GIS, demonstrate the most intense Cr(VI) occurrence is linked to cation exchange with Na-clays at depth. Cation exchange allows dissolution of Mn-bearing dolomite, which in turn produces Mn oxides in otherwise dolomite-saturated groundwaters. Mn oxides in turn are known to oxidize Cr(III) to Cr(VI). In general, co-occurrence of Mn-bearing carbonates and exchangeable clays in any aquifer, particularly those with Cr(III) present in iron oxide cements, serve as ingredients for groundwater occurrences of oxidizable trace metals.

Integrating SANS and fluid-invasion methods to characterize pore structure of typical American shale oil reservoirs.

An integration of small-angle neutron scattering (SANS), low-pressure N2 physisorption (LPNP), and mercury injection capillary pressure (MICP) methods was employed to study the pore structure of four oil shale samples from leading Niobrara, Wolfcamp, Bakken, and Utica Formations in USA. Porosity values obtained from SANS are higher than those from two fluid-invasion methods, due to the ability of neutrons to probe pore spaces inaccessible to N2 and mercury. However, SANS and LPNP methods exhibit a similar pore-size distribution, and both methods (in measuring total pore volume) show different results of porosity and pore-size distribution obtained from the MICP method (quantifying pore throats). Multi-scale (five pore-diameter intervals) inaccessible porosity to N2 was determined using SANS and LPNP data. Overall, a large value of inaccessible porosity occurs at pore diameters <10 nm, which we attribute to low connectivity of organic matter-hosted and clay-associated pores in these shales. While each method probes a unique aspect of complex pore structure of shale, the discrepancy between pore structure results from different methods is explained with respect to their difference in measurable ranges of pore diameter, pore space, pore type, sample size and associated pore connectivity, as well as theoretical base and interpretation.

Lead adsorption by biochar under the elevated competition of cadmium and aluminum.

Competitive adsorption studies are important to accurately estimate the lead adsorption capacity on biochar in soil. The structure of biochars was evaluated by Fourier-Transform Infrared Spectroscopy and X-ray Diffraction, and the competitive of Cadmium (Cd) and Aluminum (Al) with Lead (Pb) adsorption were determined by kinetic experiments and pH effects. Adsorption kinetics indicated that the adsorption amount (mg g-1) of Pb by biochar was in the decreasing order of CM400 (90.9) > BB600 (56.5) > CM100 (29.2), the presence of the oxygen-containing functional groups, Si-containing mineral, PO43- and CO32- significantly contributed to Pb adsorption by biochars. With the presence of Cd, Pb adsorption amount was reduced by 42.6%, 23.7% and 19.3% for CM100, CM400 and BB600, respectively. The Si-containing mineral, PO43- and CO32- that were rich in CM400 and BB600 has led to less competition by Cd. In addition, Al showed a strong competition with Pb leading to the adsorption being reduced by 95.8%, 82.3% and 80.6%, respectively for CM100, CM400 and BB600. This was mainly attributed to the additional acidification effect by Al resulting in a counteractive of biochar's liming effect. Results from this study are important for accurately estimating the heavy metal adsorption by biochar in soil.

An evaluation of water quality in private drinking water wells near natural gas extraction sites in the Barnett Shale formation.

Natural gas has become a leading source of alternative energy with the advent of techniques to economically extract gas reserves from deep shale formations. Here, we present an assessment of private well water quality in aquifers overlying the Barnett Shale formation of North Texas. We evaluated samples from 100 private drinking water wells using analytical chemistry techniques. Analyses revealed that arsenic, selenium, strontium and total dissolved solids (TDS) exceeded the Environmental Protection Agency's Drinking Water Maximum Contaminant Limit (MCL) in some samples from private water wells located within 3 km of active natural gas wells. Lower levels of arsenic, selenium, strontium, and barium were detected at reference sites outside the Barnett Shale region as well as sites within the Barnett Shale region located more than 3 km from active natural gas wells. Methanol and ethanol were also detected in 29% of samples. Samples exceeding MCL levels were randomly distributed within areas of active natural gas extraction, and the spatial patterns in our data suggest that elevated constituent levels could be due to a variety of factors including mobilization of natural constituents, hydrogeochemical changes from lowering of the water table, or industrial accidents such as faulty gas well casings.

Low pore connectivity in natural rock.

As repositories for CO(2) and radioactive waste, as oil and gas reservoirs, and as contaminated sites needing remediation, rock formations play a central role in energy and environmental management. The connectivity of the rock's porespace strongly affects fluid flow and solute transport. This work examines pore connectivity and its implications for fluid flow and chemical transport. Three experimental approaches (imbibition, tracer concentration profiles, and imaging) were used in combination with network modeling. In the imbibition results, three types of imbibition slope [log (cumulative imbibition) vs. log (imbibition time)] were found: the classical 0.5, plus 0.26, and 0.26 transitioning to 0.5. The imbibition slope of 0.26 seen in Indiana sandstone, metagraywacke, and Barnett shale indicates low pore connectivity, in contrast to the slope of 0.5 seen in the well-connected Berea sandstone. In the tracer profile work, rocks exhibited different distances to the plateau porosity, consistent with the pore connectivity from the imbibition tests. Injection of a molten metal into connected pore spaces, followed by 2-D imaging of the solidified alloy in polished thin sections, allowed direct assessment of pore structure and lateral connection in the rock samples. Pore-scale network modeling gave results consistent with measurements, confirming pore connectivity as the underlying cause of both anomalous behaviors: imbibition slope not having the classical value of 0.5, and accessible porosity being a function of distance from the edge. A poorly connected porespace will exhibit anomalous behavior in fluid flow and chemical transport, such as a lower imbibition slope (in air-water system) and diffusion rate than expected from classical behavior.

Uranium release from different size fractions of sediments in Hanford 300 area, Washington, USA.

Stirred-flow cell tests were carried out to investigate uranium (U) release from different size fractions of sediments from the U.S. Department of Energy's Hanford 300 Area in Washington, USA. Results show that the measured concentration of U release varies with different size fractions, with the fine-grained mass fractions (<75 µm, 75-500 µm, and 500-2000 µm) being the main U carriers. However, because the sediment is mainly composed of gravel (2000-8000 µm) materials, the gravel fraction is a non-negligible U pool. Our elution experiments give a value of 8.7% of the total U being in the gravel fraction, significantly reducing the current uncertainty in evaluating U inventory. A log-log plot of released U concentration vs. elution volume (i.e., elution time) shows a power-law relationship for all size fractions, with identical exponents for the three fine size fractions (-0.875). For the <2000 µm mass fraction, comparing our eluted U values with reported total U concentrations, we estimate that a lower bound value 8.6% of the total uranium is labile. This compares well with the previously published value of 11.8% labile U after extraction with a dilute extractant for three weeks.

Quantitative 3-D elemental mapping by LA-ICP-MS of a basaltic clast from the Hanford 300 Area, Washington, USA.

Laser ablation with inductively coupled plasma-mass spectrometry (LA-ICP-MS) was used to measure elemental concentrations at the 100-µm scale in a 3-dimensional manner within a basaltic clast sample collected from the Hanford 300 Area in south-central Washington State, United States. A calibration method was developed to quantify the LA-ICP-MS signal response using a constant-sum mass fraction of eight major elements; the method produced reasonable concentration measurements for both major and trace elements when compared to a standard basalt sample with known concentrations. 3-Dimensional maps (stacked 2-D contour layers, each representing 2100 µm × 2100 µm) show relatively uniform concentration with depth for intrinsic elements such as Si, Na, and Sr. However, U and Cu accumulation were observed near the sample surface, consistent with the site's release history of these contaminants. U and Cu show substantial heterogeneity in their concentration distributions within horizontal slices, while the intrinsic elements are essentially uniformly distributed. From these measured U concentrations and published grain size distributions, gravel and cobbles were estimated to contain about 1% of the contaminant U, implicating the coarse fraction as a long-term release source.

Fractionation and speciation of arsenic in fresh and combusted coal wastes from Yangquan, northern China.

In this study, the content and speciation of arsenic in coal waste and gas condensates from coal waste fires were investigated, respectively, using the digestion and sequential extraction methods. The fresh and fired-coal waste samples were collected from Yangquan, which is one of the major coal production regions in northern China. High-performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS) was used to determine the concentrations of four major arsenic species [As(III), As(V), monomethylarsonic acid (MMA) and dimethylarsenic acid (DMA)] in the extracts, while ICP-MS was used to measure total As content. Arsenic content in the investigated coal wastes and the condensate ranges between 23.3 and 69.3 mg/kg, which are higher than its reported average content in soils. Arsenic in coal waste exists primarily in the residual fraction; this is followed in decreasing order by the organic matter-bound, Fe-Mn oxides-bound, exchangeable, carbonates-bound, and water-soluble fractions. The high content of arsenic in the condensates indicates that combustion or spontaneous combustion is one of the major ways for arsenic release into the environment from coal waste. About 15% of the arsenic in the condensate sample is labile and can release into the environment under leaching processes. The water extractable arsenic (WEA) in the fresh coal waste, fired coal wastes, and the condensate varied between 14.6 and 341 µg/kg, with As(V) as the major species. Furthermore, both MMA and DMA were found in fresh coal wastes, fired coal wastes, and the condensate.

Using stable lead isotopes to trace heavy metal contamination sources in sediments of Xiangjiang and Lishui Rivers in China.

Lead isotopes and heavy metal concentrations were measured in two sediment cores sampled in estuaries of Xiangjiang and Lishui Rivers in Hunan province, China. The presence of anthropogenic contribution was observed in both sediments, especially in Xiangjiang sediment. In the Xiangjiang sediment, the lower (206)Pb/(207)Pb and higher (208)Pb/(206)Pb ratio, than natural Pb isotope signature (1.198 and 2.075 for (206)Pb/(207)Pb and (208)Pb/(206)Pb, respectively), indicated a significant input of non-indigenous Pb with low (206)Pb/(207)Pb and high (208)Pb/(206)Pb. The corresponding concentrations of heavy metals (As, Cd, Zn, Mn and Pb) were much higher than natural values, suggesting the contaminations of heavy metals from extensive ore-mining activities in the region.

Effects of anion competitive adsorption on arsenic enrichment in groundwater.

Long-term intake of high arsenic groundwater has caused serious endemic disease on people in Datong Basin, northern China. The high arsenic groundwater has medium to high alkalinity with a mean pH value of 8.1; the water generally belongs to HCO(3)-Na type water and contains HPO(4)(2-) in most samples. In this study, batch experiments and geochemical modeling were conducted to reveal the geochemical processes responsible for arsenic enrichment in the groundwater due to desorption, and to examine the effect of pH, phosphate, bicarbonate and silicate on this desorption in the studied groundwater system. The experimental pH ranging from 7.35 to 8.72 as observed in the high arsenic groundwater, was favorable for arsenic desorption from the aquifer sediments. Arsenic concentration in the aqueous phase significantly increased with the increase of added PO(4)(3-) concentration. An elevated arsenic content of 13.6 µg/L was observed with the highest phosphate loading of 30 mg/L. Although bicarbonate addition caused less desorption of arsenic than phosphate on the mole basis, an elevated arsenic concentration of 56 µg/L in the batch solutions was observed when the added bicarbonate contents was up to 1500 mg/L. The contribution of silicate to arsenic desorption is lower than that of phosphate and bicarbonate.

Detection of tritium sorption on four soil materials.

In order to measure groundwater age and design nuclear waste disposal sites, it is important to understand the sorption behavior of tritium on soils. In this study, batch tests were carried out using four soils from China: silty clays from An County and Jiangyou County in Sichuan Province, both of which could be considered candidate sites for Very Low Level Waste disposal; silty sand from Beijing; and loess from Yuci County in Shanxi Province, a typical Chinese loess region. The experimental results indicated that in these soil media, the distribution coefficient of tritium is slightly influenced by adsorption time, water/solid ratio, initial tritium specific activity, pH, and the content of humic and fulvic acids. The average distribution coefficient from all of these influencing factors was about 0.1-0.2 mL/g for the four types of soil samples. This relatively modest sorption of tritium in soils needs to be considered in fate and transport studies of tritium in the environment.

Sources of anthropogenic radionuclides in the environment: a review.

Studies of radionuclides in the environment have entered a new era with the renaissance of nuclear energy and associated fuel reprocessing, geological disposal of high-level nuclear wastes, and concerns about national security with respect to nuclear non-proliferation. This work presents an overview on sources of anthropogenic radionuclides in the environment, as well as a brief discussion of salient geochemical behavior of important radionuclides. We first discuss the following major anthropogenic sources and current developments that have lead, or could potentially contribute, to the radionuclide contamination of the environment: (1) nuclear weapons program; (2) nuclear weapons testing; (3) nuclear power plants; (4) uranium mining and milling; (5) commercial fuel reprocessing; (6) geological repository of high-level nuclear wastes that include radionuclides might be released in the future, and (7) nuclear accidents. Then, we briefly summarize the inventory of radionuclides (99)Tc and (129)I, as well as geochemical behavior for radionuclides (99)Tc, (129)I, and (237)Np, because of their complex geochemical behavior, long half-lives, and presumably high mobility in the environment; biogeochemical cycling and environment risk assessment must take into account speciation of these redox-sensitive radionuclides.

Arsenate toxicity for wheat and lettuce in six Chinese soils with different properties.

To assess soil arsenic (As, in the form of arsenate) toxicity to plants, 6-d root elongation tests on wheat (Triticum aestivum L.) and lettuce (Lactuca sativa) were conducted in six Chinese soils freshly spiked with As. Plants were treated with 7 or 10 levels of As to establish concentration-effect curves. Median effective concentration and 10% effective concentration values were derived with regression analysis to measure As toxic potencies, and no-observed-effect concentration was determined by comparison with a control to elucidate thresholds of As to the two plant species. The median effective concentration values for As varied from 159 to 683 mg/kg for wheat and 59 to 426 mg/kg for lettuce, and the 10% effective concentration values varied from 79 to 270 mg/kg for wheat and 20 to 156 mg/kg for lettuce. The result suggests that lettuce is a more sensitive species for monitoring soil As contamination. With the same level of As spiked, soil toxicity for a plant showed a tendency of fluvoaquic soil toward red soil or black soil toward paddy soil. The phytotoxicity of As was negatively correlated with soil amorphous iron content extracted with ammonium oxalate. The overall results from the present work illustrate the necessity of considering soil properties in assessing soil As contamination.

Accumulation of polycyclic aromatic hydrocarbons and heavy metals in lettuce grown in the soils contaminated with long-term wastewater irrigation.

Accumulation of polycyclic aromatic hydrocarbons (PAHs) and heavy metals (HMs) by crop plants from contaminated soils may pose health risks. A greenhouse pot experiment using lettuce (Lactuca satuva L.) as a representative vegetable was conducted to assess the concentrations of PAHs and HMs in vegetables grown in wastewater-contaminated soils. The concentrations of total PAHs were ranged from 1.5 to 3.4 mg kg(-1) in the contaminated soils, while 1.2 mg kg(-1) in the reference soil. Linear regression analyses showed that the relationships between soil and shoot PAH concentrations were stronger for LMW-PAHs (R(2) between 0.51 and 0.92) than for HMW-PAHs (R(2) 0.02 and 0.60), suggesting that translocation for LMW-PAHs is faster than HMW-PAHs. Furthermore, the data imply that root uptake was the main pathway for HMW-PAHs accumulation. The plant shoots were also highly contaminated with HMs, particularly Cd (0.4-0.9 mg kg(-1)), Cr (3.4-4.1 mg kg(-1)), Ni (11.7-15.1 mg kg(-1)) and Pb (2.3-5.3 mg kg(-1)), and exceed the guidance limits set by State Environmental Protection Administration (SEPA), China and the World Health Organization (WHO). This study highlights the potential health risks associated with cultivation and consumption of leafy vegetables on wastewater-contaminated soils.

Wheat phytotoxicity from arsenic and cadmium separately and together in solution culture and in a calcareous soil.

The toxicity of two toxic elements, arsenic (As) and cadmium (Cd) (individually or in combination) on root elongation of wheat seedlings (Triticum aestivum, L.) were investigated both in hydroponics and in soils freshly spiked with the toxic elements. Median effective concentration (EC(50)) and non-observed effect concentration (NOEC) were used to investigate the toxic thresholds and potencies of the two elements. The EC(50) for As was 0.97 microM in hydroponics and 196 mgkg(-1) in soil, and 4.32 microM and 449 mgkg(-1) for Cd, respectively. Toxic unit (TU) and additive index (AI) concepts were introduced to determine the combined outcomes, and different behaviors were obtained: synergism in solution culture (EC(50 mix)=0.36 TU(mix) and AI: 1.76) and antagonism in soil experiments (EC(50 mix)=1.49 TU(mix) and AI: -0.33). Furthermore, the data of soil bioavailable As and Cd cannot explain the discrepancy between the results derived from soil and hydroponics experiments.

Sorption and transport of iodine species in sediments from the Savannah River and Hanford Sites.

Iodine is an important element in studies of environmental protection and human health, global-scale hydrologic processes and nuclear nonproliferation. Biogeochemical cycling of iodine is complex, because iodine occurs in multiple oxidation states and as inorganic and organic species that may be hydrophilic, atmophilic, and biophilic. In this study, we applied new analytical techniques to study the sorption and transport behavior of iodine species (iodide, iodate, and 4-iodoaniline) in sediments collected at the Savannah River and Hanford Sites, where anthropogenic (129)I from prior nuclear fuel processing activities poses an environmental risk. We conducted integrated column and batch experiments to investigate the interconversion, sorption and transport of iodine species, and the sediments we examined exhibit a wide range in organic matter, clay mineralogy, soil pH, and texture. The results of our experiments illustrate complex behavior with various processes occurring, including iodate reduction, irreversible retention or mass loss of iodide, and rate-limited and nonlinear sorption. There was an appreciable iodate reduction to iodide, presumably mediated by the structural Fe(II) in some clay minerals; therefore, careful attention must be given to potential interconversion among species when interpreting the biogeochemical behavior of iodine in the environment. The different iodine species exhibited dramatically different sorption and transport behavior in three sediment samples, possessing different physico-chemical properties, collected from different depths at the Savannah River Site. Our study yielded additional insight into processes and mechanisms affecting the geochemical cycling of iodine in the environment, and provided quantitative estimates of key parameters (e.g., extent and rate of sorption) for risk assessment at these sites.