Arsenic bio-accessibility and bioaccumulation in aged pesticide contaminated soils: A multiline investigation to understand environmental risk.

Bio-accessibility and bioavailability of arsenic (As) in historically As-contaminated soils (cattle tick pesticide), and pristine soils were assessed using 3 different approaches. These approaches included human bio-accessibility using an extraction test replicating gastric conditions (in vitro physiologically-based extraction test); an operationally defined bioaccessibility extraction test - 1.0M HCl extraction; and a live organism bioaccumulation test using earthworms. A sequential extraction procedure revealed the soil As-pool that controls bio-accessibility and bioaccumulation of As. Findings show that As is strongly bound to historically contaminated soil with a lower degree of As bio-accessibility (<15%) and bioaccumulation (<9%) compared with freshly contaminated soil. Key to these lower degrees of bio-accessibility and bioaccumulation is the greater fraction of As associated with crystalline Fe/Al oxy-hydroxide and residual phases. The high bio-accessibility and bioaccumulation of freshly sorbed As in pristine soils were from the exchangeable and specifically sorbed As fractions. Arsenic bioaccumulation in earthworms correlates strongly with both the human bio-accessible, and the operationally defined bioavailable fractions. Hence, results suggest that indirect As bioavailability measures, such as accumulation by earthworm, can be used as complementary lines of evidence to reinforce site-wide trends in the bio-accessibility using in vitro physiologically-based extractions and/or operationally defined extraction test. Such detailed knowledge is useful for successful reclamation and management of the As contaminated soils.

Arsenic solid-phase speciation and reversible binding in long-term contaminated soils.

Historic arsenic contamination of soils occurs throughout the world from mining, industrial and agricultural activities. In Australia, the control of cattle ticks using arsenicals from the late 19th to mid 20th century has led to some 1600 contaminated sites in northern New South Wales. The effect of aging in As-mobility in two dip-site soil types, ferralitic and sandy soils, are investigated utilizing isotopic exchange techniques, and synchrotron X-ray adsorption spectroscopy (XAS). Findings show that historic soil arsenic is highly bound to the soils with >90% irreversibly bound. However, freshly added As (either added to historically loaded soils or pristine soils) has a significantly higher degree of As-accessibility. XAS data indicates that historic soil arsenic is dominated as Ca- (svenekite, & weilite), Al-(mansfieldite), and Fe- (scorodite) like mineral precipitates, whereas freshly added As is dominated by mineral adsorption surfaces, particularly the iron oxy-hydroxides (goethite and hematite), but also gibbsite and kaolin surfaces. SEM data further confirmed the presence of scorodite and mansfieldite formation in the historic contaminated soils. These data suggest that aging of historic soil-As has allowed neoformational mineral recrystallisation from surface sorption processes, which greatly reduces As-mobility and accessibility.

Evaluation of Legacy Phosphorus Storage and Release from Wetland Soils.

To better manage legacy phosphorus (P) in watersheds, reliable techniques to predict P storage and release from uplands, ditches, streams, and wetlands must be developed. Techniques such as the P saturation ratio (PSR) and the soil P storage capacity (SPSC), originally developed for upland soils, are hypothesized to be applicable to wetland soils as well. Surface soils were collected from eight beef ranches within the Lake Okeechobee Watershed, FL, to obtain a threshold PSR value and to evaluate the use of PSR and SPSC for identifying legacy P storage and release from wetland soils. Water-soluble P (WSP) was determined for all soils; the equilibrium P concentration (EPC) was determined for selected soils through the generation of Langmuir isotherms. The threshold PSR for wetland soils, calculated from P, Fe, and Al in a Mehlich 1 solution, was determined to be 0.1; SPSC, calculated using the threshold PSR, was found to be related to WSP. When SPSC was positive, WSP and EPC were minimal. However, both WSP and EPC increased once SPSC became negative. Organic matter (OM) varied from 0.4 to 90 g kg for both positive and negative SPSC, suggesting that OM in wetland soils does not have any effect on P retention and release below the threshold PSR. Moreover, when a wetland or drainage ditch is heavily P impacted, it could be a P source; wetland vegetation may no longer be able to assimilate additional P, resulting in P loss from the soil. This study suggests that the PSR-SPSC concept could be a valuable tool for evaluating legacy P release from wetlands.

Removal of radium from groundwater using a modified bauxite refinery residue.

Radium (Ra) removal by an unconventional sorbent, a modified bauxite refinery residue (MBRR), is investigated for a groundwater extracted in Missouri, USA. The MBRR treatment causes substantial reductions of both gross α and combined Ra activities from 0.955 ± 0.005 and 0.66 ± 0.005 Bq L to below detection limits (0.037 Bq L or 1 pCi L). Column breakthrough occurs at 0.555 Bq L for gross α and 0.185 Bq L for combined Ra (15 and 5 pCi L; USEPA's maximum contaminant levels) after 54 and 40 d run time, respectively. At 84 d the MBRR media continues to remove 24.3% of raw water gross α and 39.7% of the combined Ra. The treatment effluent has an initial pH of 10.9, outside the USEPA guides (6.5-8.5); this may be readily mitigated by posttreatment acid injection, or by raw water blending. The MBRR simultaneously removes other potentially hazardous trace elements (e.g., Cu, Zn, and Fe) to extremely low concentrations. In addition, toxicity characteristic leaching procedure testing of spent MBRR suggests that metals are bound tightly, such that it is nonhazardous, permitting cost-effective disposal to landfill without special confinement or storage. Consequently, MBRR may be utilized as an alternative adsorbent for treating Ra-contaminated groundwater.

The pH-dependence and reversibility of uranium and thorium binding on a modified bauxite refinery residue using isotopic exchange techniques.

The pH-dependence and reversibility of uranium and thorium binding onto a modified bauxite refinery residue (MBRR) were studied in laboratory uptake/leaching experiments. Natural (238)U and (232)Th isotopes were contacted with MBRR in an 8day loading period (equilibrium pH≈8.5) then leached in pH-dependent experiments, where the pH was decreased from 8 to 3 over several hours following addition of exchange isotopes (232)U and (229)Th. Relative concentrations of the thorium isotope pair ((232)Th and (229)Th) indicate that Th is very strongly bound to MBRR, and although at pH 3, some de-sorption is observed (232)Th (≈3%) and (229)Th (≈2.5%), released thorium is partially re-adsorbed during an overnight equilibration. During the initial equilibration, approximately 50% of the (238)U was adsorbed, and a U adsorption maximum occurs between pH 5 and pH 6, where <0.5% of the U remains in solution. However, at a pH between 5 and 3, some 60% of the bound U releases, hence the pH range of maximum U retention on the MBRR is relatively narrow. When equilibrated overnight, the MBRR releases additional U, suggesting a kinetically controlled de-sorption linked to mineral dissolution. Plots of U isotope exchange between (232)U and (238)U are linear, and suggest that U adsorption is mostly reversible. Data for adsorption in mixed systems of U and Th suggest that Th and U compete for similar binding sites.

Alkalinity conversion of bauxite refinery residues by neutralization.

Red mud remains the largest environmental issue for the alumina industry due to its high pH (>13), fine-grained nature (>90% is <10 microm), elevated sodium concentration (>50 g/kg), and soluble alkalinity (approximately 30 g/kg as equivalent CaCO(3)), which reduce the transport and reuse options of red mud. The neutralization of red mud provides potential reuse options because neutralization lowers pH, increases grain-size (e.g., coagulation), and precipitates or converts alkalinity. This paper investigates the geochemistry of 3 treatments of a red mud to affect neutralization and potentially convert materials from a waste material to a resource. This study investigates two commonly used neutralization techniques, a CO(2)-neutralized red mud (CNRM), a Basecon-neutralized red mud (Basecon), and a more novel approach of a CO(2)-neutralization followed by a Basecon-neutralization (Hybrid) to understand the effects that these treatments have on neutralization process. Data indicate that the neutralization techniques form two distinct geochemical groups when discriminated on total alkalinity alone, that is treatments with, and treatments without alkalinity precipitation. However, each treatment has distinct alkalinity speciation (hydroxide-dominant or carbonate/bicarbonate dominant) and residual Ca, Mg and Al in the treatment solution. Similarly, solids produced differ in their reaction pH and ANC, and contrary pH and ANC, a contrary to other studies, Dawsonite was not seen to precipitate during any neutralization. However, despite this approximately 17 g/kg CO(2) was sequestered during CNRM and hybrid neutralizations and all treatments increased either the transport or reuse options of red mud in some way.

Development of indices to predict phosphorus release from wetland soils.

The U.S. Environmental Protection Agency created the Clean Water Action Plan to develop nutrient criteria for four water body types: lakes and reservoirs, rivers and streams, estuaries, and wetlands. Significant progress has been made in open water systems. However, only areas in and around the Florida Everglades have had numeric nutrient criteria set, due to the complexity, heterogeneity, and limited information available for wetlands. Our objective was to evaluate various soil tests to predict significant P release potential of soil in wetlands. A total of 630 surface soil samples (0-10 cm) were collected for this study from four southeastern states: Florida, Alabama, Georgia, and South Carolina. Soil samples were collected from the center of wetlands, the edge of the wetlands, and from adjacent uplands. The phosphorus saturation ratios (PSR), calculated using P, Fe, and Al molar concentrations from Mehlich 1 (M1-PSR), Mehlich 3 (M3-PSR), and oxalate (Ox-PSR) extractions and the amount of P extracted by different extractants were used to predict P loss potential from a soil. Total phosphorus (TP) concentration in wetland soils, estimated as the 75th percentile of the distribution of least impacted wetland soils as an example, was approximately 550 mg kg(-1). Based on this reference background condition, procedures for obtaining threshold values for P release to the surrounding water bodies were developed and threshold values calculated: M1-P = 24 mg kg(-1), M3-P = 44 mg kg(-1), Ox-PSR = 0.079, M1-PSR = 0.101, and M3-PSR = 0.067.

The relationship between plasma MMP-1, -7, -8 and -13 levels and embolic potential during carotid endoluminal intervention.

BACKGROUND: Patients undergoing carotid endoluminal intervention are at risk of embolic stroke even with the use of distal protection devices. Matrix metalloproteinases (MMPs) have been implicated as a causal factor in plaque instability leading to spontaneous embolisation. We investigated whether plasma MMP levels correlated with the embolisation during carotid endoluminal intervention. METHODS: Thirty circumferentially intact carotid endarterectomy specimens were subjected to a standardised angioplasty procedure in a pulsatile ex vivo model. Emboli collected in a series of distal filters were counted and sized. Plasma samples were collected pre-operatively and analysed for MMP-7 and MMP-8 levels using Western immunoblotting. MMP-1 and MMP-13 levels were determined using ELISA. Emboli number and maximum size were correlated with plasma levels of the MMPs using Spearmans rank. RESULTS: Total MMP-8 levels were related to maximum embolus size (r=0.442, p=0.005) but not emboli number (r=0.342, p=0.052). MMP-1, -7 and -13 were not correlated with either emboli number or with maximum embolus size. CONCLUSION: Pre-operative plasma MMP-8 levels are related to the size of emboli from plaques during carotid endovascular intervention. Further in vivo studies need to be performed to assess the importance of this finding. There is potential for development of plasma markers to identify those patients at greater risk of embolic stroke during carotid endoluminal intervention.

Carotid angioplasty in a pulsatile flow model: factors affecting embolic potential.

OBJECTIVES: Carotid endoluminal intervention is an alternative to surgery but carries a risk of embolic stroke even with distal protection devices. We investigated the clinical features and degree of stenosis related to number and size of emboli during carotid angioplasty. DESIGN: An experimental ex vivo study. MATERIALS: An ex vivo pulsatile flow model was used in which temperature, velocity, flow, pressure and viscosity characteristics were designed to simulate the carotid circulation. METHODS: Carotid endarterectomy specimens excised as intact cylinders (n = 28) were subjected to a standardised angioplasty procedure using radiological guidance. Emboli collected in filters placed distally were counted and sized using microscopy. RESULTS: Median number of emboli during angioplasty was 133 (range 15-1331). Median size of the largest embolus was 700 microns (range 75-2400). Severity of stenosis correlated with increased maximum size (r = 0.55, p = 0.012). Statin therapy >4 weeks pre-operatively was associated with reduced emboli number and size (54 (range 15-748) vs 247 (range 37-1331) [p = 0.023] and 400 microm (range 75-2400) vs 1300 microm (range 600-2200) [p = 0.022]). CONCLUSIONS: In this model a wide range of emboli number and size were produced. Number and size of embolic particles were highest in patients with high-grade stenoses not receiving statin therapy.

Nebulized sildenafil is a selective pulmonary vasodilator in lambs with acute pulmonary hypertension.

OBJECTIVE: To determine whether inhalation of aerosolized sildenafil with and without inhaled nitric oxide (NO) causes selective pulmonary vasodilation in a sheep model of pulmonary hypertension. DESIGN: A controlled laboratory study in instrumented, awake, spontaneously breathing lambs. SETTING: Animal research laboratory affiliated with a university hospital. SUBJECT: Twenty Suffolk lambs. INTERVENTIONS: Lambs were instrumented with a carotid artery catheter, a pulmonary artery catheter, and a tracheostomy tube and studied awake. After baseline measurements, pulmonary hypertension was induced by the continuous infusion of U46619, a thromboxane A2 analog. After breathing three concentrations of inhaled NO (2, 5, and 20 ppm), lambs were divided into two groups. Group 1 (n = 7) breathed aerosols containing 1, 10, and 30 mg of sildenafil alone, and group 2 (n = 4) simultaneously breathed NO (2 and 5 ppm) and aerosols containing 10 mg of sildenafil. Hemodynamic measurements were obtained before and at the end of each drug administration. Venous admixture was calculated, and plasma cyclic guanosine monophosphate and sildenafil concentrations were measured. MEASUREMENTS AND MAIN RESULTS: Aerosols containing 10 mg and 30 mg of sildenafil selectively decreased the pulmonary artery pressure by 21% +/- 3% and 26% +/- 3%, respectively (p < .05 vs. baseline pulmonary hypertension). When 10 mg of sildenafil was inhaled while simultaneously breathing 2 ppm and 5 ppm NO, the pulmonary artery pressure decreased by 35% +/- 3% and 43% +/- 2% (p < .05 vs. baseline pulmonary hypertension). Inhaled sildenafil did not impair systemic oxygenation, increase right-to-left intrapulmonary shunting, or impair the ability of inhaled NO to reduce right-to-left shunting. CONCLUSIONS: Nebulized sildenafil is a selective pulmonary vasodilator that can potentiate the pulmonary vasodilating effects of inhaled NO.

Selective chemical extraction and grainsize normalisation for environmental assessment of anoxic sediments: validation of an integrated procedure.

An integrated selective extraction and size normalisation procedure for use in metal partitioning and diagenetic studies of anoxic sediments and soils is presented. Data obtained by this procedure can readily be combined with other primary data (e.g. sulfur concentrations, carbonate concentrations, cation exchange capacity, etc.) and derived parameters (e.g. degrees of pyritisation and sulfidisation) that enhance interpretation of the behaviour of trace metals in anoxic sediments. Achieving size normalisation during extraction, allows direct comparison of sediments from dissimilar sedimentary environments, and simplifies assessment of the processes that determine whether a sediment is a source of or a sink for trace metals. Aspects of a study of trace metals in sediments from the Brisbane River estuary, Australia, are used to illustrate applications of the integrated procedure.

Sildenafil is a pulmonary vasodilator in awake lambs with acute pulmonary hypertension.

BACKGROUND: Phosphodiesterase type 5 (PDE5) hydrolyzes cyclic guanosine monophosphate in the lung, thereby modulating nitric oxide (NO)/cyclic guanosine monophosphate-mediated pulmonary vasodilation. Inhibitors of PDE5 have been proposed for the treatment of pulmonary hypertension. In this study, we examined the pulmonary and systemic vasodilator properties of sildenafil, a novel selective PDE5 inhibitor, which has been approved for the treatment of erectile dysfunction. METHODS: In an awake lamb model of acute pulmonary hypertension induced by an intravenous infusion of the thromboxane analog U46619, we measured the effects of 12.5, 25, and 50 mg sildenafil administered via a nasogastric tube on pulmonary and systemic hemodynamics (n = 5). We also compared the effects of sildenafil (n = 7) and zaprinast (n = 5), a second PDE5 inhibitor, on the pulmonary vasodilator effects of 2.5, 10, and 40 parts per million inhaled NO. Finally, we examined the effect of infusing intravenous l-NAME (an inhibitor of endogenous NO production) on pulmonary vasodilation induced by 50 mg sildenafil (n = 6). RESULTS: Cumulative doses of sildenafil (12.5, 25, and 50 mg) decreased the pulmonary artery pressure 21%, 28%, and 42%, respectively, and the pulmonary vascular resistance 19%, 23%, and 45%, respectively. Systemic arterial pressure decreased 12% only after the maximum cumulative sildenafil dose. Neither sildenafil nor zaprinast augmented the ability of inhaled NO to dilate the pulmonary vasculature. Zaprinast, but not sildenafil, markedly prolonged the duration of pulmonary vasodilation after NO inhalation was discontinued. Infusion of l-NAME abolished sildenafil-induced pulmonary vasodilation. CONCLUSIONS: Sildenafil is a selective pulmonary vasodilator in an ovine model of acute pulmonary hypertension. Sildenafil induces pulmonary vasodilation via a NO-dependent mechanism. In contrast to zaprinast, sildenafil did not prolong the pulmonary vasodilator action of inhaled NO.

Avascular necrosis after treatment of DDH: the protective influence of the ossific nucleus.

We retrospectively reviewed the results of open or closed reduction for developmental dysplasia of the hip (DDH) in 49 children younger than 12 months old, who had 57 hip dislocations. Group A (18 hips) developed partial or complete avascular necrosis (AVN), and group B (39 hips) did not develop AVN. Thirty-eight hips were treated by closed reduction, and 17 had open reduction. One patient with bilateral hip dislocation initially had closed reductions followed by bilateral open reduction 3 months later. With the numbers available for study, there was no significant difference in the occurrence of AVN with respect to variables such as preliminary traction, closed versus open reduction, Pavlik harness use, and age at the time of operative intervention. However, the presence of the ossific nucleus before reduction, detected either by radiographs (p < 0.001) or ultrasonography (p = 0.033) was statistically significant in predicting AVN. Only one (4%) of 25 hips with an ossific nucleus developed AVN, whereas 17 (53%) of 32 hips without an ossific nucleus before reduction developed AVN. Our results suggest that the presence of the ossific nucleus before closed or open reduction for DDH may decrease the risk of AVN.

Management implications of metal transfer pathways from a refuse tip to mangrove sediments.

Mangroves have often been thought of as wasteland, and because of this attitude, many mangrove forests have been used as sites for refuse tips, sewage outfalls and as illegal dumping grounds. The transfer of metals from a refuse tip to mangrove sediments is investigated and four pathways of heavy metal migration are identified. These are direct seepage across the tip-cell floor to groundwater, tidal over-topping of the bund wall and capillary suction of leachates to groundwaters, direct seepage through the cell wall of leachates to surficial sediments, and surface runoff during rainfall events. Metal input by surficial runoff indicates that significant quantities of metals have been transferred to the mangroves via this mechanism. However, metal transfer via surface runoff is probably small in comparison to the other three mechanisms discussed. The variable nature of the transfer mechanisms operating, the variability in sediment texture both vertically and laterally, and the number of transfer pathways makes potential management of the site difficult. Any management plan for this site must consider both the feedback mechanisms that operate, and that the whole sediment column is involved in metal transfer.

The physically challenged athlete.

Several studies note that the relative risk of injury for physically challenged athletes is approximately the same as that of nondisabled athletes. Since the 1940s physically challenged athletes have increasingly competed on national and international levels. This chapter describes sport-specific adaptations (such as a prosthesis or wheelchair), classifies the suitability of sports activities according to disability, and outlines measures to prevent injury in disabled athletes. The author also includes a resource list of publications, organizations, and web sites for disabled athletes.

Literature and ethical medicine: five cases from common practice.

This essay is composed of five stories written by practicing physicians about their patients. Each clinical story describes a challenging ethical condition-potential abuse of medical power, gravely ill and probably over-treated newborns, iatrogenic narcotic addiction, deceived dying people. Rather than singling out one ethical conflict to resolve or adjudicate, the authors attempt, through literary methods, to grasp the singular experiences of their patients and to act according to the deep structures of their patients' lives. Examining these five stories with simple literary tools-attention to narrative frames, time, plot, and desire-reveals the mechanisms through which acts of writing and reading contribute to clinical clarity and ethical actions.

The nucleotide sequence of chromosome I from Saccharomyces cerevisiae.

Chromosome I from the yeast Saccharomyces cerevisiae contains a DNA molecule of approximately 231 kbp and is the smallest naturally occurring functional eukaryotic nuclear chromosome so far characterized. The nucleotide sequence of this chromosome has been determined as part of an international collaboration to sequence the entire yeast genome. The chromosome contains 89 open reading frames and 4 tRNA genes. The central 165 kbp of the chromosome resembles other large sequenced regions of the yeast genome in both its high density and distribution of genes. In contrast, the remaining sequences flanking this DNA that comprise the two ends of the chromosome and make up more than 25% of the DNA molecule have a much lower gene density, are largely not transcribed, contain no genes essential for vegetative growth, and contain several apparent pseudogenes and a 15-kbp redundant sequence. These terminally repetitive regions consist of a telomeric repeat called W', flanked by DNA closely related to the yeast FLO1 gene. The low gene density, presence of pseudogenes, and lack of expression are consistent with the idea that these terminal regions represent the yeast equivalent of heterochromatin. The occurrence of such a high proportion of DNA with so little information suggests that its presence gives this chromosome the critical length required for proper function.

Site-directed mutagenesis of the yeast PRP20/SRM1 gene reveals distinct activity domains in the protein product.

Prp20/Srm1, a homolog of the mammalian protein RCC1 in Saccharomyces cerevisiae, binds to double-stranded DNA (dsDNA) through a multicomponent complex in vitro. This dsDNA-binding capability of the Prp20 complex has been shown to be cell-cycle dependent; affinity for dsDNA is lost during DNA replication. By analyzing a number of temperature sensitive (ts) prp20 alleles produced in vivo and in vitro, as well as site-directed mutations in highly conserved positions in the imperfect repeats that make up the protein, we have determined a relationship between the residues at these positions, cell viability, and the dsDNA-binding abilities of the Prp20 complex. These data reveal that the essential residues for Prp20 function are located mainly in the second and the third repeats at the amino-terminus and the last two repeats, the seventh and eighth, at the carboxyl-terminus of Prp20. Carboxyl-terminal mutations in Prp20 differ from amino-terminal mutations in showing loss of dsDNA binding: their conditional lethal phenotype and the loss of dsDNA binding affinity are both suppressible by overproduction of Gsp1, a GTP-binding constituent of the Prp20 complex, homologous to the mammalian protein TC4/Ran. Although wild-type Prp20 does not bind to dsDNA on its own, two mutations in conserved residues were found that caused the isolated protein to bind dsDNA. These data imply that, in situ, the other components of the Prp20 complex regulate the conformation of Prp20 and thus its affinity for dsDNA. Gsp1 not only influences the dsDNA-binding ability of Prp20 but it also regulates other essential function(s) of the Prp20 complex. Overproduction of Gsp1 also suppresses the lethality of two conditional mutations in the penultimate carboxyl-terminal repeat of Prp20, even though these mutations do not eliminate the dsDNA binding activity of the Prp20 complex. Other site-directed mutants reveal that internal and carboxyl-terminal regions of Prp20 that lack homology to RCC1 are dispensable for dsDNA binding and growth.

LTE1 of Saccharomyces cerevisiae is a 1435 codon open reading frame that has sequence similarities to guanine nucleotide releasing factors.

The DNA sequence of the LTE1 gene on the left arm of chromosome I of Saccharomyces cerevisiae has been determined. The LTE1 open reading frame comprises 4305 bp that can be translated into 1435 amino acid residues. The position of this open reading frame corresponds well to that of a 4.7 kb transcript that has been mapped to this position. The derived amino acid sequence has significant similarities to the amino acid sequence of the guanine nucleotide releasing factor isolated from a rat brain library. The carboxy-terminus of the LTE1 protein also shows similarities to other guanine nucleotide exchange factors of the S. cerevisiae CDC25 family.