Diffusion in Porous Rock Is Anomalous.

Molecular diffusion of chemical species in subsurface environments─rock formations, soil sediments, marine, river, and lake sediments─plays a critical role in a variety of dynamic processes, many of which affect water chemistry. We investigate and demonstrate the occurrence of anomalous (non-Fickian) diffusion behavior, distinct from classically assumed Fickian diffusion. We measured molecular diffusion through a series of five chalk and dolomite rock samples over a period of about two months. We demonstrate that in all cases, diffusion behavior is significantly different than Fickian. We then analyze the results using a continuous time random walk framework that can describe anomalous diffusion in heterogeneous porous materials such as rock. This methodology shows extreme long-time tailing of tracer advance as compared to conventional Fickian diffusion processes. The finding that distinct anomalous diffusion occurs ubiquitously implies that diffusion-driven processes in subsurface zones should be analyzed using tools that account for non-Fickian diffusion.

Amniotic fluid rubidium concentration association with newborn birthweight: a maternal-neonatal pilot study.

BACKGROUND: Although most biological systems, including human tissues, contain rubidium, its biogeochemical functions and possible role in neonatal birthweight are largely unknown. An animal study indicated a correlation between rubidium deficiency in the maternal diet and lower newborn birthweight. OBJECTIVE: This pilot study measured rubidium concentrations in amniotic fluid during the second trimester of (low-risk) pregnancy and investigated potential correlations between rubidium levels and third-trimester newborn birthweight-small for gestational age, appropriate for gestational age, and large for gestational age-and between preterm birth and term birth in uncomplicated pregnancies. STUDY DESIGN: This prospective, single-center study investigated a possible relationship between rubidium concentration in second-trimester amniotic fluid and third-trimester birthweight percentile. Amniotic fluid (at a median gestational age of 19 weeks) was sampled to determine rubidium concentration. Maternal and newborn characteristics were obtained from participant and delivery records. RESULTS: After screening 173 pregnant women, 99 amniotic fluid samples were evaluated. Midpregnancy median rubidium concentrations were significantly lower among newborns that were classified as small for gestational age than among newborns that were classified as appropriate for gestational age (106 vs 136 µg/L; P<.01). Based on a logistic regression random forest model, amniotic fluid rubidium was identified as a significant contributing factor to appropriate-for-gestational-age birthweight with 54% of the total contribution. CONCLUSION: Amniotic fluid rubidium concentration seems to be a strong predictor of appropriate-for-gestational-age birthweight and a potential marker for newborn birthweight classifications. In particular, low rubidium concentrations in amniotic fluid during midpregnancy are linked to third-trimester lower birthweight percentile. These findings could potentially serve as a valuable tool for early identification of pregnancy outcomes. Further investigation is necessary to fully explore the effect of rubidium on fetal development.

The Impact of Radiographic, Metabolic and Demographic Characteristics on Kidney Stone Recurrence.

Urolithiasis is a frequent disease with cited rates of recurrence after initial diagnosis that vary widely and range between 35% and 50%. We assessed the radiographic recurrence rate in patients with urinary stones and its risk factors. We retrospectively identified patients who were diagnosed with urinary stones on non-contrast computed tomography from 2010 to 2011, and underwent another imaging examination at least six months afterwards. We collected patient demographic, clinical, laboratory and radiologic data and compared patients with and without urinary stone recurrence. Ultimately, 237 patients were included in the study; the mean follow-up was 6.7 years; 88 patients (37.1%) had recurrence based on our recurrence criteria. On univariate analysis, the significant parameters for recurrence were baseline serum calcium and uric acid, stone location in the kidney, surgical intervention and stone burden volume. On multivariate analysis, surgical intervention (OR 3.07, p = 0.001), baseline calcium (OR 2.56, p = 0.011), baseline uric acid (OR 1.30, p = 0.021) and stone location in the kidney (OR 2.16, p = 0.012) were associated with higher risk of recurrence. These findings may guide personalized follow-up protocols for patients with urolithiasis based on their risk factors.

Mobility and Retention of Rare Earth Elements in Porous Media.

There is growing concern that rare earth elements (REEs) will become emerging soil-water contaminants because of their increased use in new technologies and products, which may lead to unavoidable release to the environment. To better understand the environmental behavior of REEs, a comprehensive set of adsorption and column transport experiments was conducted in quartz sand media. The retention and mobility of three representative REEs (La, Gd, and Er) were studied in the presence and absence of humic acid (HA; 5, 20, and 50 mg L-1) and under a range of pH conditions (5-8). Results show that REE mobility and retention are controlled by the amount of REE-HA complexes formed in a solution, which increases with increasing HA concentrations and solution pH. Gadolinium is the most mobile among the representative REEs, followed by Er and La, corresponding to the amount of (calculated) REE-HA complexes. Increasing HA concentrations in the REE solution inhibits REE retention in both the batch adsorption and column experiments. The same retardation trend was observed for lower HA concentrations (Gd > Er > La). In a fixed HA concentration, HA and REE adsorption decrease simultaneously as the solution pH increases, indicating the co-adsorption of REEs and HA on the sand. Scanning electron microscopy detection of elongated regions attached to the sand, where high REE and carbon (HA) concentrations were measured, further suggests the co-adsorption of REE-HA complexes. Modeling the column experiments shows that the time-dependent attachment is dominant at high HA concentrations, while at lower HA concentrations, both the time-dependent and spontaneous attachments play equal roles. These results provide a quantitative characterization of REE retention and mobility in sand media.

Drainage of infected kidneys with ureteral stents: does size matter?

PURPOSE: The purpose of our study was to evaluate the ability of ureteral stents with different diameters to drain pus that accumulates in an obstructed kidney using an in vitro model. METHODS: We developed an in vitro model of an obstructed kidney filled with pus. The model included a silicon kidney unit based on computed tomography (CT) data, a 3D printed ureteral stone based on a real extracted ureteral stone, a latex ureter model, a bladder vessel, and a fluid with qualities resembling pus. Identical printed stones were inserted into four ureter models containing stents with varying diameters (4.8F, 6F, 7F, 8F), each of which was connected to the kidney unit and the bladder vessel. The kidney unit was filled with artificial pus to pressures of 30 cmH2O to simulate an infected and obstructed kidney. The obstruction was relieved with stents in place, while artificial urine was pumped into the kidney; pressure in the kidney and remaining pus were measured continuously. RESULTS: The rate of pressure drop and the final pressure measured in the kidney were unaffected by the diameter of the stent. For all stent diameters, the pressure reached non-obstructed levels within 30 s, final pressure was reached within 90-120 s, and minimal amounts of pus remained in the kidney after 120 min. CONCLUSIONS: In vitro experiments demonstrate that all stent diameters drain pus-filled, obstructed kidneys with the same efficacy. The common perception that larger diameter tubes are more effective under such circumstances should be re-examined.

Magnetic resonance imaging of in vitro urine flow in single and tandem stented ureters subject to extrinsic ureteral obstruction.

OBJECTIVE: To quantify the relative volumetric flows in stent and ureter lumina, as a function of stent size and configuration, in both unobstructed and externally obstructed stented ureters. METHODS: Magnetic resonance imaging was used to measure flow in stented ureters using a phantom kidney model. Volumetric flow in the stent and ureter lumina were determined along the stented ureters, for each of four single stent sizes (4.8F, 6F, 7F, and 8F), and for tandem (6F and 7F) configurations. Measurements were made in the presence of a fully encircling extrinsic ureteral obstruction as well as in benchmark cases with no extrinsic ureteral obstruction. RESULTS: Under no obstruction, the relative contribution of urine flow in single stents is 1-10%, while the relative contributions to flow are ~6 and ~28% for tandem 6F and 7F, respectively. In the presence of an extrinsic ureteral obstruction and single stents, all urine passes within the stent lumen near the extrinsic ureteral obstruction. For tandem 6F and 7F stents under extrinsic ureteral obstruction, relative volumetric flows in the two stent lumina are ~73% and ~81%, respectively, with the remainder passing through the ureter lumen. CONCLUSIONS: Magnetic resonance imaging demonstrates that with no extrinsic ureteral obstruction, minimal urine flow occurs within a stent. Stent lumen flow is significant in the presence of extrinsic ureteral obstruction, in the vicinity of the extrinsic ureteral obstruction. For tandem stents subjected to extrinsic ureteral obstruction, urine flow also occurs in the ureter lumen between the stents, which can reduce the likelihood of kidney failure even in the case of both stent lumina being occluded.

Imaging and Chemical Analysis of External and Internal Ureteral Stent Encrustation.

Introduction: Ureteral stents are effective in alleviating flow disruptions in the urinary tract, whether due to ureteral stones, strictures or extrinsic ureteral obstruction. However, significant stent encrustation on the external and/or internal stent lumen walls can occur, which may interfere with stent functioning and/or removal. Currently, there is only limited, generally qualitative, information on the distribution, mineral structure, and chemical content of these deposits, particularly in terms of stent lumen encrustation. Objective: To quantify, in an initial investigation, external and internal encrustation in representative, intact ureteral stents. The study investigates possible correlations between patterns of external and internal encrustation, determines mineral structure and chemical composition, and examines the potential for stent lumen obstruction even in the absence of external stent wall encrustation. Study Design: High-resolution, laboratory micro-computed tomography (micro-CT) was used to non-destructively image external and internal stent encrustation in four representative stents. X-ray diffractometry (XRD) and scanning electron microscopy-energy dispersive x-ray spectroscopy (SEM-EDS) enabled parallel analysis of mineral structure and chemical content of samples collected from external and internal encrusted material along the distal, proximal and mid-ureteral stent regions. Results: Extensive stent lumen encrustation can occur within any region of a stent, with only incidental or minor external encrustation, along the entire length of the stent. External and internal encrusted materials in a given stent are generally similar, consisting of a combination of amorphous (mostly organic) and crystalline mineral deposits. Conclusion: Micro-CT demonstrates that significant stent lumen encrustation can occur, which can lead to partial or full stent lumen occlusion, even when the exterior stent wall is essentially free of encrusted material.

Influence of Single Stent Size and Tandem Stents Subject to Extrinsic Ureteral Obstruction and Stent Occlusion on Stent Failure.

Background and Purpose: Drainage of obstructed kidney attributable to extrinsic ureteral obstruction (EUO), required to prevent renal damage, is often achieved using Double-J ureteral stents. However, these stents fail frequently, and there is considerable debate regarding what stent size, type, and configuration offer the best option for sustained drainage. In this study, we examine the impact of stent diameter and choice of single/tandem configuration, subject to EUO and various degrees of stent occlusion, on stent failure. Materials and Methods: Computational fluid dynamics simulations and an in vitro ureter-stent experiment enabled quantification of flow behavior in stented ureters subject to EUO and stent occlusions. Various single and tandem stents under EUO were considered. In each simulation and experiment, changes in renal pressure were monitored for different degrees of stent lumen occlusion, and onset of stent failure as well as simulated distributions of fluid flow between stent and ureter lumina were determined. Results: For an encircling EUO that completely obstructs the ureter lumen, with or without partial stent occlusion, the choice of stent size/configuration has little effect on renal pressure. The pressure increases significantly for ∼90% stent lumen occlusion, with failure at >95% occlusion, independent of stent diameter or a tandem configuration, and with little influence of occlusion length along the stent. Conclusions: Stent failure rate is independent of stent diameter or single/tandem configuration, for the same percentage of stent lumen occlusion, in this model. Stent failure incidence may decrease for larger diameter stents and tandem configurations, because of the larger luminal area.

Electronic waste as a source of rare earth element pollution: Leaching, transport in porous media, and the effects of nanoparticles.

Rare earth elements (REEs) are an emerging pollutant whose increasing use in various technological applications causes increasing risk of environmental contamination. Electronic waste (E-waste) could be one major source of REE pollution, as E-waste typically contains elevated REE concentrations and is often handled in unsafe and environmentally hazardous ways. Here, a series of leaching assays revealed that <1% of REEs available in a representative E-waste were released except at acidic conditions (pH 2) rarely observed in nature. If REEs are leached from E-waste, the extent of their spread in the environment will depend, in large part, on their mobility through porous media. Measurements of REE transport through saturated sand demonstrated extremely limited mobility except at acidic conditions (pH 2), though significant REE retention by the substrate still occurs at this low pH. Similar experiments in a natural soil found REE mobility to be even lower in that substrate, with complete REE retention even after the passage of up to 215 pore volumes of a 500 ppb REE solution. Aqueous REEs are therefore not expected to be highly mobile in the environment. The presence of natural or anthropogenic nanoparticles may affect REE behavior during leaching and/or transport. Measurements indicated that silica nanoparticles can increase the concentration of fluid-mobile REEs during E-waste leaching, but both plastic and silica nanoparticles have a negligible effect on REE transport. Ultimately, the experiments and analysis presented here suggest that the threat of REE pollution from E-waste is minimal except at specific sites with unusual environmental conditions.

The Human Impact on All Soil-Forming Factors during the Anthropocene.

Soil-the thin outer skin of the Earth's land-is a critical and fragile natural resource. Soil is the basis for almost all global agriculture and the medium in which most terrestrial biological activity occurs. Here, we reconsider the five forming factors of soil originally suggested more than a century ago (parent material, time, climate, topography, and organisms) and updated over the years to add human activity as the sixth forming factor. We demonstrate how present anthropogenic activity has become the leading component influencing each one of the original forming factors. We thus propose that, starting from the Anthropocene, human activity should no longer be considered as a separate forming factor but rather a main driving force of each of the five original ones. We suggest that the importance of soil and the strong direct and indirect effects of anthropogenic factors on soil-forming factors should be considered together to ensure sustainability of this critical resource.

Comparative study of renal drainage with different ureteral stents subject to extrinsic ureteral obstruction using an in vitro ureter-stent model.

BACKGROUND: To compare the efficacy of different ureteral stents subject to extrinsic ureteral obstruction (EUO), in a controlled in vitro stented ureter experiment. METHODS: We employ an in vitro ureter-stent experimental set-up, with latex tubing simulating flexible ureters attached to vessels simulating renal units and bladders. The flow behavior of five ureteral stents-polymeric 8F, tandem 6F, tandem 7F, endopyelotomy and metal-was tested under a ureteral deformation configuration of 40°, with 2000 g external force over a 3.5 cm length of the ureter. A constant fluid flow was applied through the ureter-stent configurations, and pressure fluctuations in the renal unit were monitored. We considered a renal unit pressure of 10 cmH2O or flow discontinuation in the bladder as stent failure. Urine containing debris was mimicked by use of a colloidal solution. RESULTS: Of all assessed ureteral stents, under EUO conditions, only the single 8F stents remained patent throughout the length of the experiment. All other stents-tandem 6F and 7F, single 7F, metal and endopyelotomy-displayed limitations. CONCLUSIONS: Tandem and metal stents show no superiority over large luminal polymeric stents for EUO treatment in this in vitro model. Larger luminal stents offer excellent resistance to external pressure and allow adequate colloidal flow. The need for frequent exchange and bladder irritation should also be considered in the choice of stent configuration for treatment of kidney drainage under EUO.

Selected technology-critical elements as indicators of anthropogenic groundwater contamination.

Groundwater contamination originating from anthropogenic industrial activities is a global concern, adversely impacting health of living organisms and affecting natural ecosystems. Monitoring contamination in a complex groundwater system is often limited by sparse data and poor hydrogeological delineation, so that numerous indicators (organic, inorganic, isotopic) are frequently used simultaneously to reduce uncertainty. We suggest that selected Technology-Critical Elements (TCEs), which are usually found in very low concentrations in the groundwater environment, might serve as contamination indicators that can be monitored through aquifer systems. Here, we demonstrate the use of selected TCEs (in particular, Y, Rh, Tl, Ga, and Ge) as indicators for monitoring anthropogenic groundwater contamination in two different groundwater systems, near the Dead Sea, Israel. Using these TCEs, we show that the sources of local groundwater contamination are phosphogypsum ponds located adjacent to fertilizer plants in two industrial areas. In addition, we monitored the spatial distribution of the contaminant plume to determine the extent of well and spring contamination in the region. Results show significant contamination of the groundwater beneath both fertilizer plants, leading to contamination of a series of wells and two natural springs. The water in these springs contains elevated concentrations of toxic metals; U and Tl levels, among others, are above the maximum concentration limits for drinking water.

Do organic substances act as a degradable binding matrix in calcium oxalate kidney stones?

BACKGROUND: Calcium oxalate (CaOx) stones are considered to be highly resistant to chemolysis. While significant organic matter has been identified within these stones, which is presumed to bind (inorganic) CaOx particles and aggregates, most chemolysis efforts have focused on methods to attack the CaOx components of a stone. We examine the feasibility of inducing chemolysis of CaOx kidney stones, within hours, by specifically attacking the organic matrix present in these stones. METHODS: In contrast to previous studies, we focused on the possible "brick and mortar" stone configuration. We systematically tested, via in vitro experiments, the ability of an extensive range of 26 potential chemolysis agents to induce relatively fast disintegration (and/or dissolution) of a large set of natural CaOx stone fragments, extracted during endourological procedures, without regard to immediate clinical application. Each stone fragment was monitored for reduction in weight and other changes over 72 h. RESULTS: We find that agents known to attack organic material have little, if any, effect on stone chemolysis. Similarly, protein and enzymatic agents, and oral additive medical treatments, have little immediate effect. CONCLUSIONS: These findings suggest that the organic and inorganic constituents present in CaOx stones are not structured as "brick and mortar" configurations in terms of inorganic and organic components.

Failure of ureteral stents subject to extrinsic ureteral obstruction and stent occlusions.

PURPOSE: To quantify the occurrence of stent failure and the dynamic behavior of urine flow in ureter-stent systems, including the relative flow in the ureter and stent lumina, subject to various degrees of ureter and stent blockage. METHODS: Numerical simulations based on computational fluid dynamics (CFD) were used to quantify urine flow behavior in stented ureters, in the presence of extrinsic ureteral obstruction (EUO) and stent occlusions. Two stented ureter configurations were considered, one with circumferential occlusion of the ureter and the second with pressure on one side of the ureter wall. The pressure within the renal unit for different degrees of ureter closure and stent lumen occlusion was determined systematically. Onset of stent failure and the distribution of urine flow between stent and ureter lumina were determined. RESULTS: In the case of EUO completely encircling the ureter, causing 100% obstruction of the ureter lumen, pressure in the renal unit is essentially unaffected until the stent lumen reaches ~ 90% occlusion, and fails only with > 95% occlusion. Occlusions of 50% in stent side holes in the vicinity of the EUO only alter local flow patterns but have no significant influence on renal unit pressure. For EUO deforming and compressing the ureter from one side, with ~ 50% reduction in ureter lumen, urine drainage proceeds with negligible increase in renal pressure even with 100% occlusion in the stent lumen. CONCLUSION: CFD simulations show that stent failure under EUO tends to occur suddenly, only when both ureter and stent lumina become almost fully blocked.

Effects of particle size and surface chemistry on plastic nanoparticle transport in saturated natural porous media.

Plastic nanoparticles (PNPs) are considered contaminants of emerging concern, but little information is available on their transport behavior in the soil-water environment, as well as their behavior relative to metal and other carbon-based nanoparticles. Here we show that size and surface functional groups affect the transport of polystyrene nanoparticles (PS-NPs) through saturated soil. Unmodified 110 nm and 50 nm PS-NPs demonstrated similar transport patterns in soil. However, a maximum elution value of 90% from the soil was found for the 50 nm PS-NPs, compared to a maximum value of ∼45% for 110 nm PS-NPs. The breakthrough curve for 190 nm PS-NPs demonstrated a maximum elution value of 60% from the soil. PS-NPs with surface functional groups display different mobility profiles: carboxylated PS-NPs demonstrated a plateau of 40% elution from the soil, while aminated PS-NPs were eluted only in small amounts and showed a spike pattern of elution from the column. These findings are attributed to the effects of common soil constituents such as calcium cations and humic acids on the size and charge of the PS-NPs with surface functional groups. Overall, PS-NP mobility in soil can vary widely, depending on PNP properties such as size and surface chemistry, and on matrix properties, such as the type of porous medium and its composition. These findings suggest that knowledge of inherent characteristics (size, surface charge, surface functional groups) of PNPs are required to elucidate the behavior of such particles in soil-water environments, and predict the extent of contaminant spreading.

Impact of Colloidal Fluid on Stent Failure Under Extrinsic Ureteral Obstruction: An In Vitro Experimental Study.

Background and Purpose: Drainage of an obstructed kidney due to extrinsic ureteral obstruction (EUO) is imperative. Ureteral stents, commonly employed to facilitate drainage, often fail under EUO; this is usually attributed to external pressure over the ureter that occludes the stent lumen. We showed previously that external pressure and deformation of the ureter, alone, cannot explain frequent stent failure and speculated that colloids present in urine may play a critical synergetic role. In this study, we evaluate the role of colloidal fluid in ureteral obstruction under extrinsic compression. Materials and Methods: An in vitro ureter-stent model was employed using a latex tube to simulate a flexible ureter connecting simulated glass kidney and bladder units. The ureter was placed in deformed configuration of 40° with external pressure of 2000 g exerted over the deformed region of the stented ureter, representing extrinsic pressure. Four different ureteral stents were tested-4.8F, 6F, 7F, and 8F. Colloidal solution based on chicken albumin was injected through the simulated kidney into the stented ureter. Four replicates were performed for each stent diameter and straight stented ureters with no external pressure were used as controls. Stent failure was defined as kidney unit pressure over 10 cmH2O or complete obstruction of fluid flow; time to stent failure was measured. Results: Average failure time in 4.8F and 6F stents was 44 and 66 hours, respectively. The 7F ureteral stent failed in two replicates, after an average time of 75 hours, and continued to drain in the other two replicates. The 8F and control stents showed no change in kidney unit pressure in any of the replicates. Conclusions: Large-diameter stents are more effective in ureteral drainage under EUO in the presence of colloidal material in the fluid. Colloidal fluid may have a role in stent failure under EUO.

Elucidating the catalytic degradation of enrofloxacin by copper oxide nanoparticles through the identification of the reactive oxygen species.

Copper oxide nanoparticles (CuO-NPs) have been suggested as effective catalysts to degrade many persistent organic contaminants. In parallel, CuO-NPs are considered toxic to soil microorganisms, plants and human cells, possibly because they induce oxidative stress and generation of reactive oxygen species (ROS). However, the mechanism of the catalytic process and the generated ROS are poorly understood. Here we discuss the reaction mechanism of CuO-NPs during the catalytic degradation of enrofloxacin - an antibiotic pharmaceutical used in this study as a representative persistent organic compound. The degradation of an aqueous solution of the enrofloxacin exposed to CuO-NPs and hydrogen peroxide was studied showing fast removal of the enrofloxacin at ambient conditionsns. ROS production was identified by electron spin resonance and a spin trapping technique. The distribution of the free radical species indicated production of a high percentage of superoxide (O2-.) radicals as well as hydroxyl radicals; this production is similar to the "radical production" activity of the superoxide dismutase (SOD) enzyme in the presence of hydrogen peroxide. This activity was also tested in the opposite direction, to examine if CuO-NPs show reactivity that potentially mimics the classical SOD enzymatic activity. The CuO-NPs were found to catalyze the dismutation of superoxide to hydrogen peroxide and oxygen in a set of laboratory experiments.

Influence of humic substances on the transport of indium and gallium in porous media.

Indium and gallium are used widely in modern industry, mostly for the production of semiconductors. They are considered as Technology-Critical Elements and have therefore received growing attention in the past few years. We investigated the influence of different types of humic substances on the transport of indium and gallium in laboratory-scale, saturated column experiments, to gain understanding of their mobility in natural environments. We evaluated the effect of different humic substances on the transport of indium and gallium in quartz sand: a commercial humic acid (Aldrich Humic Acid, AHA), a fulvic acid (Suwannee River Fulvic Acid, SRFA) and an aquatic natural organic matter (Suwannee River Natural Organic Matter, SRNOM). The impact of the flow rate and the influence of different concentrations of organic matter were also investigated. Indium was shown to be more mobile than gallium in the presence of humic substances. The mobility of indium in sand was highest for SRNOM, followed by SRFA and then AHA, while for gallium the order was SRFA > SRNOM > AHA. These results can be significant in understanding the mobility of indium and gallium in soils with various compositions of organic matter.