Mineral carbonate dissolution with increasing CO2 pressure measured by underwater laser induced breakdown spectroscopy and its application in carbon sequestration.

In this study, the ability of laser-induced breakdown spectroscopy (LIBS) to measure the in situ aqueous dissolution of various mineral carbonates with increasing CO2 pressure was examined. Dissolution experiments included four geologically common mineral carbonates (CaCO3, MgCO3, MnCO3, SrCO3) and the CO2 pressure ranged from ambient to 250 bar. The ensuing plasma emission was spectrally analyzed, and the intensities of Ca, Mg, Mn, and Sr emission lines were used to monitor the respective metal cations released to the aqueous solution. The strong emission lines of Ca (Ca II 393.36, Ca II 396.84, Ca I 422.67 nm), Mg (unresolved magnesium doublet: Mg I 383.230, Mg I 383.829 nm), Mn (unresolved manganese triplet: Mn I 403.076, Mn I 403.307, Mn I 403.449 nm), and Sr (Sr II 407.77, Sr II 421.55, Sr I 460.73 nm) were identified in the spectra. The amounts of metals released from their respective carbonates were estimated at different time intervals following the CO2 injection (5 m, 1, 2, 3, 4, 24 h) and at different pressures (50, 100, 150, 200, 250 bar) using calibration models developed at corresponding pressure settings. The results demonstrated that the pressure-induced dissolution of all carbonates was consistent with their expected and selective pH-dependent solubility. The dissolution rate of CaCO3, MgCO3, and SrCO3 was found to be higher than that of MnCO3. The dissolution of constituents in a Mt. Simon sandstone associated with a deep saline reservoir at elevated CO2 pressure was also studied and Ca release was quantified. The results demonstrated that real-time monitoring of carbonate dissolution by LIBS may provide a useful indirect detection system indicative of CO2 leakage from geologic carbon storage sites.

Determination of Rare Earth Elements in Geological Samples Using Laser-Induced Breakdown Spectroscopy (LIBS).

Laser-induced breakdown spectroscopy (LIBS) was used to detect rare earth elements (REEs) in natural geological samples. Low and high intensity emission lines of Ce, La, Nd, Y, Pr, Sm, Eu, Gd, and Dy were identified in the spectra recorded from the samples to claim the presence of these REEs. Multivariate analysis was executed by developing partial least squares regression (PLS-R) models for the quantification of Ce, La, and Nd. Analysis of unknown samples indicated that the prediction results of these samples were found comparable to those obtained by inductively coupled plasma mass spectrometry analysis. Data support that LIBS has potential to quantify REEs in geological minerals/ores.

Analysis of charcoal blast furnace slags by laser-induced breakdown spectroscopy.

Laser-induced breakdown spectroscopy (LIBS) was used for the analysis of charcoal blast furnace slags. Plasma was generated by an application of a 1064 nm wavelength Nd:YAG laser beam to the surface of pellets created from the slags. The presence of Al, Ca, Fe, K, Mg, Mn, and Si was determined by identifying their characteristic spectral signatures. Multivariate analysis was performed for the quantification of these elements. The predicted LIBS results were found in agreement with the inductively coupled plasma optical emission spectrometry analysis. The limit of detection for Al, Ca, Fe, K, Mg, Mn, and Si was calculated to be 0.10%, 0.22%, 0.02%, 0.01%, 0.01%, 0.005%, and 0.18%, respectively.

Influence of CO2 pressure on the emission spectra and plasma parameters in underwater laser-induced breakdown spectroscopy.

Optical emission spectroscopic studies have been carried out to investigate the pressure effect of CO2 on laser-produced underwater plasma. The plasma was generated by focusing 1064 nm, 6 ns pulses from a Nd:YAG laser in a CO2-bearing solution. The temporal evolution of the continuum emission, Sr and Ba lines, and plasma electron density and temperature was characterized under CO2 pressure ranging from 10 to 300 bars. The electron density measurements were made using the Stark broadening of the 455.40 nm Ba II line, while the temperature measurements have been performed by the Saha-Boltzmann method using the Sr I-II lines at 460.73 and 407.77 nm, respectively. It was found that CO2 pressure has little effect on the emission line intensity and signal-to-background ratio. The electron density and the temperature are found to be independent of the CO2 pressure at early times. When time becomes longer, the electron density exhibits an appreciable rise as the CO2 pressure increases, while the temperature is found to be unchanged.

Rare earth element geochemistry of outcrop and core samples from the Marcellus Shale.

In this work, the geochemistry of the rare earth elements (REE) was studied in eleven outcrop samples and six, depth-interval samples of a core from the Marcellus Shale. The REE are classically applied analytes for investigating depositional environments and inferring geochemical processes, making them of interest as potential, naturally occurring indicators of fluid sources as well as indicators of geochemical processes in solid waste disposal. However, little is known of the REE occurrence in the Marcellus Shale or its produced waters, and this study represents one of the first, thorough characterizations of the REE in the Marcellus Shale. In these samples, the abundance of REE and the fractionation of REE profiles were correlated with different mineral components of the shale. Namely, samples with a larger clay component were inferred to have higher absolute concentrations of REE but have less distinctive patterns. Conversely, samples with larger carbonate fractions exhibited a greater degree of fractionation, albeit with lower total abundance. Further study is necessary to determine release mechanisms, as well as REE fate-and-transport, however these results have implications for future brine and solid waste management applications.

In vitro-cultured wheat spikes provide a simplified alternative for studies of cadmium uptake in developing grains.

BACKGROUND: An immature wheat spike culture system was used to monitor cadmium (Cd) accumulation in grains, hulls and awns of bread wheat and durum wheat. Immature spikes were cultured prior to anthesis in a medium containing 50 g L(-1) sucrose and 0.4 g L(-1) L-glutamine, supplemented with 0, 0.1, 0.5, 1, 2, 3, 4, 5, 10, 15, 20 or 25 mg L(-1) cadmium chloride (CdCl(2)). Grains were collected at maturity and their Cd accumulation was determined using inductively coupled plasma mass spectrometry (ICP-MS). RESULTS: Cd accumulation at CdCl(2) concentrations of 3 mg L(-1) and above was higher in grains of durum wheat compared with bread wheat. In hulls a similar trend was observed at CdCl(2) concentrations above 15 mg L(-1) . Starch concentration in grains increased slightly at 3 and 4 mg L(-1) CdCl(2). Cd accumulation negatively affected grain protein concentration. Expression patterns of Cd-related genes glutathione reductase (TaGR), metallothionein (MT) and phytochelatin synthase (PCS) in spikes cultured in media containing 0, 5, 10, 15 and 25 mg L(-1) CdCl(2) at 5 days post-anthesis showed that TaGR and PCS expression in bread wheat was up-regulated at 5 mg L(-1) CdCl(2) but down-regulated at other CdCl(2) concentrations. However, in durum wheat, expression of all three genes was down-regulated or remained unchanged. CONCLUSION: This study demonstrates that immature spike culture can be used to study Cd accumulation in grains and can delineate hyper-accumulating durum wheat from bread wheat at CdCl(2) concentrations of 2 mg L(-1) and above.

Continuous venovenous hemodiafiltration trace element clearance in pediatric patients: a case series.

Continuous renal replacement therapy (CRRT) is used to treat critically ill children with acute kidney injury. The effect of CRRT on trace element clearance is poorly characterized. The purpose of this study was to quantify the transmembrane clearance of chromium, copper, manganese, selenium and zinc during continuous venovenous hemodiafiltration (CVVHDF). The transmembrane clearance of trace elements was assessed prospectively in five critically ill children receiving CVVHDF at the pediatric intensive care unit of a tertiary care university hospital. Pre-filter blood and effluent samples were measured for trace element concentrations. Transmembrane clearance of trace elements was calculated, and daily loss of each trace element was determined. Daily trace element loss via CVVHDF was compared with daily standard supplementation of trace elements in pediatric parenteral nutrition. Five patients (age range 23 months to 15 years) with a body weight range of 10.5-53 kg completed the study. The median transmembrane clearance of chromium, copper, manganese, selenium and zinc during CVVHDF was calculated as 0 ml, 0.59 ml, 2.48 ml, 1.22 ml, and 1.90 ml, respectively, per 1.73 m(2) body surface area per minute. The calculated CVVHDF losses were substantially smaller than the daily parenteral supplementation for all trace elements.

Trace element removal during in vitro and in vivo continuous haemodialysis.

BACKGROUND: Continuous renal replacement therapy (CRRT) increasingly is being used to treat critically ill patients with renal disease. CRRT removes waste products but also nutrients. Our understanding of trace element CRRT clearance has been limited by poor assay sensitivity. The development of inductively coupled plasma mass spectrometry (ICP-MS) allows for the measurement of CRRT trace element removal. METHODS: Continuous venovenous haemodialysis (CVVHD) transmembrane clearances of trace elements and urea were assessed using a bovine blood-based in vitro model using two different haemodialyser types. These findings were validated in 10 critically ill adult patients receiving continuous venovenous haemodiafiltration (CVVHDF). Calculated daily trace element loss was compared with a typical dose of daily trace element supplementation. RESULTS: The mean +/- SD in vitro CVVHD transmembrane clearances (ml/min) for the polysulfone haemodialyser were chromium 0.97 +/- 0.23, copper 0.47 +/- 0.18, manganese 4.6 +/- 3.6, selenium 1.2 +/- 0.63 and zinc 2.3 +/- 0.32 and for the cellulose diacetate haemodialyser chromium 1.54 +/- 0.91, copper 0.21 +/- 0.07, manganese 7.8 +/- 4.1, selenium 0.76 +/- 0.39 and zinc 2.7 +/- 0.37. The in vivo CVVHDF transmembrane clearances (ml/min) were chromium 5.4 +/- 2.4, copper 0.45 +/- 0.33, manganese 1.9 +/- 4.6, selenium 1.6 +/- 1.2, and zinc 4.0 +/- 1.3. CONCLUSION: ICP-MS assays detected the five trace elements in the effluent of CVVHDF patients. Trace element CVVHD transmembrane clearance estimates for our in vitro model were supported by the in vivo CVVHDF findings. Calculated daily trace element loss attributed to CVVHD and CVVHDF with dialysate flow rates of 33.3 ml/min is less than what is provided in a daily dose of a trace element supplementation product.

Analysis of the zinc finger domain of TnpA, a DNA targeting protein encoded by mobilizable transposon Tn4555.

The mobilizable transposon Tn4555, found in Bacteroides spp., is an important antibiotic resistance element encoding a broad spectrum beta-lactamase. Tn4555 is mobilized by conjugative transposons such as CTn341 which can transfer the transposon to a wide range of bacterial species where it integrates into preferred sites on the host chromosome. Selection of the preferred target sites is mediated by a DNA-binding protein TnpA which has a prominent zinc finger motif at the N-terminus of the protein. In this report the zinc finger motif was disrupted by site directed mutagenesis in which two cysteine residues were changed to serine residues. Elemental analysis indicated that the wild-type protein but not the mutated protein was able to coordinate zinc at a molar ration of 1/1. DNA binding electrophoretic mobility shift assays showed that the ability to bind the target site DNA was not significantly affected by the mutation but there was about a 50% decrease in the ability to bind single stranded DNA. Consistent with these results, electrophoretic mobility shift assays incorporating zinc chelators did not have a significant on affect the binding of DNA target. In vivo, the zinc finger mutation completely prevented transposition/integration as measured in a conjugation assay. This was in contrast to results in which a TnpA knockout was still able to insert into host genomes but there was no preferred target site selection. The phenotype of the zinc finger mutation was not effectively rescued by providing wild-type TnpA in trans. Taken together these results indicated that the zinc finger is not required for DNA binding activity of TnpA but that it does have an important role in transposition and it may mediate protein/protein interactions with integrase or other Tn4555 proteins to facilitate insertion into the preferred sites.

In vitro clearance of trace elements via continuous renal replacement therapy.

OBJECTIVE: Trace element loss during continuous renal replacement therapy in patients with acute renal failure has not been quantified sufficiently. DESIGN: Trace element loss was quantified using an in vitro model of continuous venovenous hemofiltration. Bovine blood was used for the experiment, and the plasma was analyzed for its chromium, copper, selenium, manganese, and zinc content. Two different polysulfone hemodiafilters, a low-flux F8 and high-flux F70 were used, and tested at two different ultrafiltrate flow rates of 1 L/hr and 2 L/hr, respectively. Trace element concentrations in the plasma and ultrafiltrate were analyzed using inductively coupled plasma mass spectrometry. The sieving coefficient and clearance of each trace element were calculated and compared between the two hemodiafilters. SETTING: In vitro bovine model of continuous venovenous hemofiltration. PATIENTS OR OTHER PARTICIPANTS: Not applicable. RESULTS: Mean sieving coefficients of both F8 and F70 hemodiafilters were similar for each trace element. Copper, chromium, manganese, selenium, and zinc all were detected in the ultrafiltrate. Estimated trace element loss using typical trace element blood concentrations and study-derived sieving coefficients suggest that daily losses of selenium are greater than what is replenished with a standard daily trace element supplement in total parenteral nutrition. CONCLUSION: These data suggest that the degree of continuous venovenous hemofiltration clearance chromium, copper, selenium, manganese, and zinc differ between elements and that selenium and copper might need to be replaced with doses that exceed typical supplementation guidelines.

Enhanced accumulation of phosphate by Lolium multiflorum cultivars grown in phosphate-enriched medium.

Agricultural and animal husbandry practices combined with soil composition have caused phosphate overloading of farmlands in different parts of the U.S. and Europe. Movement of soluble phosphates (Pi) from phosphorus enriched soils results in degradation of natural aquatic systems, triggering serious environmental problems. Remediation of such sites using plants that tolerate and accumulate high concentrations of Pi in their aerial parts may be an attractive remediation technology. In the present study, Pi transport and accumulation potential of Marshall and Gulf ryegrass (Lolium multiflorum cultivars) were determined using a solution culture of seedlings. Ryegrass seedlings accumulated phosphorus (P) in excess of 2% of dry weight in their aerial parts when supplied with 5 g/L KH2PO4 in medium. Phosphorus accumulation was positively correlated with the concentration of phosphate (0-5 g/L KH2PO4) in medium. Plants grew well on medium containing 5 g/L KH2PO4, but concentrations above 5 g/L caused symptoms of toxicity. Scanning electron microscopy and energy-dispersive X-ray spectroscopy confirmed high P accumulation in different cell types of grass roots and shoots. Phosphate starvation and replenishment experiments point to the unique ability of these grasses to concentrate phosphate in the above-ground parts. It is hypothesized that the unique ability of these ryegrass cultivars may be due to the presence of efficient phosphate transport and sequestration mechanisms.

Reduced Ca2+-calmodulin-dependent protein kinase activity and expression in LV myocardium of dogs with heart failure.

Studies on the status of multifunctional Ca(2+)-calmodulin (CaM)-dependent protein kinase-II (CaMKII) in failing hearts are limited and controversial. The study was performed in the left ventricular (LV) myocardium of six dogs with heart failure (HF) (LV ejection fraction, 23 +/- 2%) and six normal (NL) dogs. In the LV homogenate, CaMKII activity and its protein level were determined by using the CaMKII peptide and antibody, respectively. Furthermore, the protein level of CaM and phosphorylated phospholamban (PLB) at threonine-17 (PLB-Thr(17)) and serine-16 (PLB-Ser(16)) were also determined in the LV homogenate using a specific antibody. In addition, the level of zinc, which inhibits protein kinase A activity, was determined in the LV tissue by inductively coupled plasma mass spectrometry. CaMKII activity and phosphorylated PLB-Thr(17) and PLB-Ser(16) levels, but not CaM and Zn levels, were significantly reduced in the LV homogenate of dogs with HF compared with NL dogs. These results suggest that CaMKII activity is reduced in the failing LV myocardium, and this abnormality is associated with reduced protein expression level of the enzyme but not due to changes in CaM and zinc levels. In conclusion, reduced CaMKII activity and phosphorylated PLB level may be partly responsible for impaired sarcoplasmic reticulum function in HF.

Scavenger receptor class B type I expression and elemental analysis in cerebellum and parietal cortex regions of the Alzheimer's disease brain.

Metal ions play an important role in health and disease by influencing cellular biochemical pathways. The increased concentrations of some metal ions may have cytotoxic effects through their ability to oxidatively modify biomolecules, which may cause oxidative stress-induced brain cell death leading to neurodegenerative disorders observed in Alzheimer's disease (AD). We therefore performed elemental analysis of human brain tissues by a sophisticated method of inductively coupled plasma mass spectrometry (ICP-MS) in two regions of the AD brain, the parietal cortex and cerebellum, and compared them with the age-matched control. Our analysis shows the differential distribution of some metal ions in the two regions of the brain. Most importantly, Si, Sn, Al and Mn showed significantly higher levels in the parietal cortex of the AD brain compared to the control. The other metal ions showing moderate increases in the parietal cortex were Na, Te, Cr, Fe and B. Since these metal ions can modify lipoproteins in the brain and modified lipoproteins are taken up by scavenger receptors class B type I (SR-BI), we also determined the presence of SR-BI in the parietal cortex and cerebellum regions of the control and AD brains using a sensitive method, the reverse transcriptase-polymerase chain reaction. Our results suggest that SR-BI are present in the parietal cortex as well as in the cerebellum of the control and AD brains, suggesting that the presence of SR-BI may be involved in the uptake of oxidatively modified lipoproteins and beta-amyloid (Abeta) protein complexed with apoE, suggesting implications in the progression of late onset AD and other neurodegenerative disorders characterized by the deposition of insoluble aggregates observed in the AD brain.