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1.
BMC Health Serv Res ; 24(1): 554, 2024 Apr 30.
Article in English | MEDLINE | ID: mdl-38693519

ABSTRACT

BACKGROUND: There is significant health inequity in the United Kingdom (U.K.), with different populations facing challenges accessing health services, which can impact health outcomes. At one London National Health Service (NHS) Trust, data showed that patients from deprived areas and minority ethnic groups had a higher likelihood of missing their first outpatient appointment. This study's objectives were to understand barriers to specific patient populations attending first outpatient appointments, explore systemic factors and assess appointment awareness. METHODS: Five high-volume specialties identified as having inequitable access based on ethnicity and deprivation were selected as the study setting. Mixed methods were employed to understand barriers to outpatient attendance, including qualitative semi-structured interviews with patients and staff, observations of staff workflows and interrogation of quantitative data on appointment communication. To identify barriers, semi-structured interviews were conducted with patients who missed their appointment and were from a minority ethnic group or deprived area. Staff interviews and observations were carried out to further understand attendance barriers. Patient interview data were analysed using inductive thematic analysis to create a thematic framework and triangulated with staff data. Subthemes were mapped onto a behavioural science framework highlighting behaviours that could be targeted. Quantitative data from patient interviews were analysed to assess appointment awareness and communication. RESULTS: Twenty-six patients and 11 staff were interviewed, with four staff observed. Seven themes were identified as barriers - communication factors, communication methods, healthcare system, system errors, transport, appointment, and personal factors. Knowledge about appointments was an important identified behaviour, supported by eight out of 26 patients answering that they were unaware of their missed appointment. Environmental context and resources were other strongly represented behavioural factors, highlighting systemic barriers that prevent attendance. CONCLUSION: This study showed the barriers preventing patients from minority ethnic groups or living in deprived areas from attending their outpatient appointment. These barriers included communication factors, communication methods, healthcare the system, system errors, transport, appointment, and personal factors. Healthcare services should acknowledge this and work with public members from these communities to co-design solutions supporting attendance. Our work provides a basis for future intervention design, informed by behavioural science and community involvement.


Subject(s)
Appointments and Schedules , Health Services Accessibility , State Medicine , Humans , London , Male , Female , Middle Aged , Adult , Qualitative Research , Interviews as Topic , Aged , Healthcare Disparities/ethnology , Minority Groups/statistics & numerical data , Minority Groups/psychology , Ethnicity/psychology , Ethnicity/statistics & numerical data , Communication
2.
Small ; 20(9): e2307611, 2024 Mar.
Article in English | MEDLINE | ID: mdl-37863821

ABSTRACT

Fullertubes, that is, fullerenes consisting of a carbon nanotube moiety capped by hemifullerene ends, are emerging carbon nanomaterials whose properties show both fullerene and carbon nanotube (CNT) traits. Albeit it may be expected that their electronic states show a certain resemblance to those of the extended nanotube, such a correlation has not yet been found or described. Here it shows a scanning tunneling microscopy (STM) and spectroscopy (STS) characterization of the adsorption, self-assembly, and electronic structure of 2D arrays of [5,5]-C90 fullertube molecules on two different noble metal surfaces, Ag(111) and Au(111). The results demonstrate that the shape of the molecular orbitals of the adsorbed fullertubes corresponds closely to those expected for isolated species on the grounds of density functional theory calculations. Moreover, a comparison between the electronic density profiles in the bands of the extended [5,5]-CNT and in the molecules reveals that some of the frontier orbitals of the fullertube molecules can be described as the result of the quantum confinement imposed by the hemifullerene caps to the delocalized band states in the extended CNT. The results thus provide a conceptual framework for the rational design of custom fullertube molecules and can potentially become a cornerstone in the understanding of these new carbon nanoforms.

4.
J Am Chem Soc ; 144(36): 16287-16291, 2022 09 14.
Article in English | MEDLINE | ID: mdl-36037095

ABSTRACT

We report the first experimental characterization of isomerically pure and pristine C120 fullertubes, [5,5] C120-D5d(1) and [10,0] C120-D5h(10766). These new molecules represent the highest aspect ratio fullertubes isolated to date; for example, the prior largest empty cage fullertube was [5,5] C100-D5d(1). This increase of 20 carbon atoms represents a gigantic leap in comparison to three decades of C60-C90 fullerene research. Moreover, the [10,0] C120-D5d(10766) fullertube has an end-cap derived from C80-Ih and is a new fullertube whose C40 end-cap has not yet been isolated experimentally. Theoretical and experimental analyses of anisotropic polarizability and UV-vis assign C120 isomer I as a [5,5] C120-D5d(1) fullertube. C120 isomer II matches a [10,0] C120-D5h(10766) fullertube. These structural assignments are further supported by Raman data showing metallic character for [5,5] C120-D5d(1) and nonmetallic character for C120-D5h(10766). STM imaging reveals a tubular structure with an aspect ratio consistent with a [5,5] C120-D5d(1) fullertube. With microgram quantities not amenable to crystallography, we demonstrate that DFT anisotropic polarizability, augmented by long-accepted experimental analyses (HPLC retention time, UV-vis, Raman, and STM) can be synergistically used (with DFT) to down select, predict, and assign C120 fullertube candidate structures. From 10 774 mathematically possible IPR C120 structures, this anisotropic polarizability paradigm is quite favorable to distinguish tubular structures from carbon soot. Identification of isomers I and II was surprisingly facile, i.e., two purified isomers for two possible structures of widely distinguishing features. These metallic and nonmetallic C120 fullertube isomers open the door to both fundamental research and application development.


Subject(s)
Fullerenes , Fullerenes/chemistry , Isomerism
5.
J Am Chem Soc ; 144(24): 10825-10829, 2022 Jun 22.
Article in English | MEDLINE | ID: mdl-35675387

ABSTRACT

We report the fully fledged photophysical characterization of isomerically pure, empty-caged, tubular fullerenes D5h-C90 and D5d-C100 and compare their key properties. In particular, the focus was on cage sizes between 60 and 150 carbon atoms with D3, D3d/h, and D5d/h symmetry. The optical band gap of D5d-C100 is 1.65 eV, which is larger than 1.37 eV of D5h-C90. In stark contrast to the nonluminescent D5h-C90, D5d-C100 luminesces at room temperature. Transient absorption spectroscopy shows that photoexcited D5d-C100 is subject to a slow intersystem crossing that generates a triplet excited state. In contrast, a fast, nonradiative internal conversion governs the deactivation of D5h-C90: In this case, exploring the corresponding triplet excited state required triplet-triplet sensitization experiments with anthracene. Density functional theory calculations revealed the electronic structure of the fullertubes, and calculations are consistent with our experimental findings. The calculated band gap systematically decreases with the number of carbon atoms within the D3 and D3d/h series. In contrast, an oscillating behavior is noted within the series of D5d/h fullertubes. Finally, photoexcited D5d-C100 was found to undergo hole transfer with electron-donating triethylamines readily but not electron transfer with electron-accepting methyl viologens.

6.
Angew Chem Int Ed Engl ; 61(21): e202116727, 2022 May 16.
Article in English | MEDLINE | ID: mdl-35254698

ABSTRACT

A new isolation protocol was recently reported for highly purified metallic Fullertubes D5h -C90 , D3d -C96 , and D5d -C100, which exhibit unique electronic features. Here, we report the oxygen reduction electrocatalytic behavior of C60 , C70 (spheroidal fullerenes), and C90 , C96 , and C100 (tubular fullerenes) using a combination of experimental and theoretical approaches. C96 (a metal-free catalyst) displayed remarkable oxygen reduction reaction (ORR) activity, with an onset potential of 0.85 V and a halfway potential of 0.75 V, which are close to the state-of-the-art Pt/C benchmark catalyst values. We achieved an excellent power density of 0.75 W cm-2 using C96 as a modified cathode in a proton-exchange membrane fuel cell, comparable to other recently reported efficient metal-free catalysts. Combined band structure (experimentally calculated) and free-energy (DFT) investigations show that both favorable energy-level alignment active catalytic sites on the carbon cage are responsible for the superior activity of C96 .

7.
Brain ; 145(1): 17-26, 2022 03 29.
Article in English | MEDLINE | ID: mdl-35265969

ABSTRACT

Accumulating evidence suggests that neurodegenerative diseases are not merely neuronal in nature but comprise multicellular involvement, with astrocytes emerging as key players. The pathomechanisms of several neurodegenerative diseases involve the deposition of misfolded protein aggregates in neurons that have characteristic prion-like behaviours such as template-directed seeding, intercellular propagation, distinct conformational strains and protein-mediated toxicity. The role of astrocytes in dealing with these pathological prion-like protein aggregates and whether their responses either protect from or conspire with the disease process is currently unclear. Here we review the existing literature implicating astrocytes in multiple neurodegenerative proteinopathies with a focus on prion-like behaviour in this context.


Subject(s)
Neurodegenerative Diseases , Prion Diseases , Prions , Astrocytes/metabolism , Humans , Neurodegenerative Diseases/pathology , Prion Diseases/pathology , Prions/metabolism , Protein Aggregates , Protein Folding
8.
Alzheimers Res Ther ; 13(1): 127, 2021 07 12.
Article in English | MEDLINE | ID: mdl-34253227

ABSTRACT

BACKGROUND: Although social cognitive dysfunction is a major feature of frontotemporal dementia (FTD), it has been poorly studied in familial forms. A key goal of studies is to detect early cognitive impairment using validated measures in large patient cohorts. METHODS: We used the Revised Self-Monitoring Scale (RSMS) as a measure of socioemotional sensitivity in 730 participants from the genetic FTD initiative (GENFI) observational study: 269 mutation-negative healthy controls, 193 C9orf72 expansion carriers, 193 GRN mutation carriers and 75 MAPT mutation carriers. All participants underwent the standardised GENFI clinical assessment including the 'CDR® plus NACC FTLD' scale and RSMS. The RSMS total score and its two subscores, socioemotional expressiveness (EX score) and modification of self-presentation (SP score) were measured. Volumetric T1-weighted magnetic resonance imaging was available from 377 mutation carriers for voxel-based morphometry (VBM) analysis. RESULTS: The RSMS was decreased in symptomatic mutation carriers in all genetic groups but at a prodromal stage only in the C9orf72 (for the total score and both subscores) and GRN (for the modification of self-presentation subscore) groups. RSMS score correlated with disease severity in all groups. The VBM analysis implicated an overlapping network of regions including the orbitofrontal cortex, insula, temporal pole, medial temporal lobe and striatum. CONCLUSIONS: The RSMS indexes socioemotional impairment at an early stage of genetic FTD and may be a suitable outcome measure in forthcoming trials.


Subject(s)
Frontotemporal Dementia , C9orf72 Protein/genetics , Frontotemporal Dementia/diagnostic imaging , Frontotemporal Dementia/genetics , Humans , Magnetic Resonance Imaging , Mutation/genetics , Progranulins/genetics , Social Cognition , tau Proteins/genetics
9.
Environ Pollut ; 283: 117232, 2021 Aug 15.
Article in English | MEDLINE | ID: mdl-34034019

ABSTRACT

Restoring woody vegetation to riparian zones helps to protect waterways from excessive sediment and nutrient inputs. However, the associated leaf litter can be a major source of dissolved organic matter (DOM) leached into surface waters. DOM can lead to the formation of disinfection by-products (DBPs) during drinking water treatment. This study investigated the DBPs formed during chlorination of DOM leached from leaf litter and assessed the potential toxicity of DBPs generated. We compared the leachate of two native Australian riparian trees, Casuarina cunninghamiana and Eucalyptus tereticornis, and a reservoir water source from a catchment dominated by Eucalyptus species. Leachates were diluted to dissolved organic carbon concentrations equivalent to the reservoir (~9 mg L-1). E. tereticornis leachates produced more trihalomethanes (THMs), haloacetic acids (HAAs), and haloketones after chlorination, while C. cunninghamiana produced more chloral hydrate and haloacetonitriles. Leachate from both species produced less THMs and more HAAs per mole of carbon than reservoir water. This may be because reservoir water had more aromatic, humic characteristics while leaf leachates had relatively more protein-like components. Using in vitro bioassays to test the mixture effects of all chemicals, chlorinated E. tereticornis leachate induced oxidative stress in HepG2 liver cells and bacterial toxicity more frequently and at lower concentrations than C. cunninghamiana and reservoir water. Overall, this study has shown that the DOM leached from litter of these species has the potential to generate DBPs and each species has a unique DBP profile with differing bioassay responses. E. tereticornis may pose a relatively greater risk to drinking water than C. cunninghamiana as it showed greater toxicity in bioassays. This implies tree species should be considered when planning riparian zones to ensure the benefits of vegetation to waterways are not offset by unintended increased DBP production and associated toxicity following chlorination at downstream drinking water intakes.


Subject(s)
Disinfectants , Water Pollutants, Chemical , Water Purification , Australia , Disinfection , Halogenation , Trihalomethanes/analysis , Trihalomethanes/toxicity , Water Pollutants, Chemical/analysis , Water Pollutants, Chemical/toxicity
10.
J Am Chem Soc ; 143(12): 4593-4599, 2021 03 31.
Article in English | MEDLINE | ID: mdl-33733775

ABSTRACT

Although fullerenes were discovered nearly 35 years ago, scientists still struggle to isolate "single molecule" tubular fullerenes larger than C90. In similar fashion, there is a paucity of reports for pristine single-walled carbon nanotubes (SWNTs). In spite of Herculean efforts, the isolation and properties of pristine members of these carbonaceous classes remain largely unfulfilled. For example, the low abundance of spherical and tubular higher fullerenes in electric-arc extracts (<0.01-0.5%) and multiplicity of structural isomers remain a major challenge. Recently, a new isolation protocol for highly tubular fullerenes, also called f ullertubes, was reported. Herein, we describe spectroscopic characterization including 13C NMR, XPS, and Raman results for purified [5,5] fullertube family members, D5h-C90 and D5d-C100. In addition, DFT computational HOMO-LUMO gaps, polarizability indices, and electron density maps were also obtained. The Raman and 13C NMR results are consistent with semiconducting and metallic properties for D5h-C90 and D5d-C100, respectively. Our report suggests that short [5,5] fullertubes with aspect ratios of only ∼1.5-2 are metallic and could exhibit unique electronic properties.

11.
Prog Neurobiol ; 200: 101973, 2021 05.
Article in English | MEDLINE | ID: mdl-33309801

ABSTRACT

Both astrocytes and microglia fulfil homeostatic and immune functions in the healthy CNS. Dysfunction of these cell types have been implicated in the pathomechanisms of several neurodegenerative diseases. Understanding the cellular autonomy and early pathological changes in these cell types may inform drug screening and therapy development. While animal models and post-mortem tissue have been invaluable in understanding disease processes, the advent of human in vitro models provides a unique insight into disease biology as a manipulable model system obtained directly from patients. Here, we discuss the different human in vitro models of astrocytes and microglia and outline the phenotypes that have been recapitulated in these systems.


Subject(s)
Microglia , Neurodegenerative Diseases , Animals , Astrocytes , Humans
12.
FEBS Lett ; 594(21): 3490-3503, 2020 11.
Article in English | MEDLINE | ID: mdl-32871611

ABSTRACT

Amyloid fibrils found in plaques in Alzheimer's disease (AD) brains are composed of amyloid-ß peptides. Oligomeric amyloid-ß 1-42 (Aß42) is thought to play a critical role in neurodegeneration in AD. Here, we determine how size and conformation affect neurotoxicity and internalisation of Aß42 assemblies using biophysical methods, immunoblotting, toxicity assays and live-cell imaging. We report significant cytotoxicity of Aß42 oligomers and their internalisation into neurons. In contrast, Aß42 fibrils show reduced internalisation and no toxicity. Sonicating Aß42 fibrils generates species similar in size to oligomers but remains nontoxic. The results suggest that Aß42 oligomers have unique properties that underlie their neurotoxic potential. Furthermore, we show that incubating cells with Aß42 oligomers for 24 h is sufficient to trigger irreversible neurotoxicity.


Subject(s)
Amyloid beta-Peptides/chemistry , Amyloid beta-Peptides/toxicity , Peptide Fragments/chemistry , Peptide Fragments/toxicity , Protein Aggregation, Pathological , Alzheimer Disease/metabolism , Alzheimer Disease/pathology , Amyloid/chemistry , Amyloid/metabolism , Amyloid/pharmacology , Amyloid/toxicity , Amyloid beta-Peptides/metabolism , Amyloid beta-Peptides/pharmacokinetics , Cell Survival/drug effects , Humans , Molecular Weight , Neurons/drug effects , Neurons/metabolism , Neurons/pathology , Peptide Fragments/metabolism , Peptide Fragments/pharmacokinetics , Protein Conformation , Sonication
13.
J Am Chem Soc ; 142(36): 15614-15623, 2020 09 09.
Article in English | MEDLINE | ID: mdl-32830484

ABSTRACT

We report a chemical separation method to isolate fullertubes: a new and soluble allotrope of carbon whose structure merges nanotube, graphene, and fullerene subunits. Fullertubes possess single-walled carbon nanotube belts resembling a rolled graphene midsection, but with half-fullerene end-caps. Unlike nanotubes, fullertubes are reproducible in structure, possess a defined molecular weight, and are soluble in pristine form. The high reactivity of amines with spheroidal fullerene cages enables their removal and allows a facile isolation of C96-D3d(3), C90-D5h(1), and C100-D5d(1) fullertubes. A nonchromatographic step (Stage 1) uses a selective reaction of carbon cages with aminopropanol to permit a highly enriched sample of fullertubes. Spheroidal fullerenes are reacted and removed by attaching water-soluble groups onto their cage surfaces. With this enriched (100-1000 times) fullertube mixture, Stage 2 becomes a simple HPLC collection with a single column. This two-stage separation approach permits fullertubes in scalable quantities. Characterization of purified C100-D5d(1) fullertubes is done with samples isolated in pristine and unfunctionalized form. Surprisingly, C60 and C100-D5d(1) are both purplish in solution. For X-ray crystallographic analysis, we used decapyrrylcorannulene (DPC). Isomerically purified C90 and C100 fullertubes were mixed with DPC to obtain black cocrystals of 2DPC{C90-D5h(1)}·4(toluene) and 2DPC{C100-D5d(1)}·4(toluene), respectively. A serendipitous outcome of this chemical separation approach is the enrichment and purification of several unreported larger carbon species, e.g., C120, C132, and C156. Isolation of these higher cage species represents a significant advance in the unknown experimental arena of C100-C200 structures. Our findings represent seminal experimental evidence for the existence of two mathematically predicted families of fullertubes: one family with an axial hexagon with the other series based on an axial pentagon ring. Fullertubes have been predicted theoretically, and herein is their experimental evidence, isolation, and initial characterization.

14.
Toxicon ; 176: 47-54, 2020 Mar.
Article in English | MEDLINE | ID: mdl-32103795

ABSTRACT

Cyanobacteria species are sensitive to many plant allelochemicals, such as pyrogallol. However, little attention has been paid to the relative effects of these xenobiotics on co-occurring toxigenic and non-toxigenic cyanobacterial strains, despite their co-existence in blooms. Hence, the responses of one toxigenic (TS2) and two non-toxigenic (NS1, NS2) Microcystis aeruginosa strains to pyrogallol were tested under three conditions: mono-culture and co-cultured either directly or separately by dialysis membrane. The study showed that the inhibitory effects of pyrogallol on the growth and photosynthetic yield (Fv/Fm) of either toxigenic or non-toxigenic M. aeruginosa strains were lower in direct and dialysis co-culture conditions than those in mono-culture conditions. This result indicated that chemical-mediated reciprocal effects occur between the co-existing toxigenic and non-toxigenic strains. The toxigenic M. aeruginosa strain was more sensitive to pyrogallol than the non-toxigenic strains in both mono- and co-culture systems, though whether this outcome is due to the former's toxigenic status is unclear. Intracellular microcystin-LR (MC-LR) concentrations of the toxigenic strain decreased after pyrogallol addition in both mono- and co-culture systems, whereas extracellular MC-LR concentrations increased. This finding may reflect the cell damage of M. aeruginosa because of the pyrogallol. At the same initial number of cells, the extracellular MC-LR concentration released from the same amount of TS2 cells in mono-culture was slightly higher than that in dialysis co-culture conditions. Overall, this study shows that plant allelochemicals may have the potential to reduce bloom toxicity by reducing the proportion of toxigenic cyanobacterial strains, and the effects of co-existing strains must be considered when assessing the effects of plant allelochemicals on target strains.


Subject(s)
Microcystins/toxicity , Microcystis/drug effects , Pyrogallol/toxicity , Cyanobacteria , Marine Toxins , Microcystis/physiology , Water Microbiology
15.
Sci Total Environ ; 703: 134530, 2020 Feb 10.
Article in English | MEDLINE | ID: mdl-31757551

ABSTRACT

Wetting of leaf litter accumulated in riparian zones during rainfall events provides pulses of dissolved organic matter (DOM) to rivers. Restoring riparian vegetation aims to reduce sediment and nutrient transport into rivers, however DOM from leaf litter can stimulate phytoplankton growth and interfere with water treatment processes. Improved understanding of the loads and chemical composition of DOM leached from leaf litter of different plant species, and how subsequent leaching through soils affects DOM retention or transformation, is needed to predict the outcomes of riparian revegetation. To investigate this, we simulated rapid leaching of rainfall through the leaf litter of two riparian tree species with and without subsequent leaching through soil, comparing dissolved organic carbon (DOC) and nitrogen (DON) loads, and DOM chemical composition (via spectroscopic and novel NMR-fingerprinting techniques). Plant source affected the load and composition of DOM leaching, with Eucalyptus tereticornis leaching more DOC than Casuarina cunninghamiana. Additionally, E. tereticornis DOM had a higher sugar, myo-inositol, benzoic acid, flavonoid and oxygenated aromatic content. More than 90% of leaf litter DOM was retained in the soil under simulated repeated heavy rainfall. The DOM chemistry of these species determined the total loads and changes in DOM composition leaching through soil. Less E. tereticornis DOM was retained by the soil than C. cunninghamiana DOM, with sugars, myo-inositol and amino acids being poorly retained compared to fatty acids and aromatic compounds. It also appears that DOM from E. tereticornis litter primed the soil, resulting in more DON being leached compared with bare soil. In comparison, C.cunninghamiana litter resulted in greater retention of DON, oxygenated aromatic compounds and the amino acid tryptophan. This study provides new information on how a range of DOM sources and transformations affect the DOM ultimately leached into waterways, key to developing improved models of DOM transformations in catchments.


Subject(s)
Plant Leaves , Soil , Carbon , Nitrogen , Trees
16.
Acta Neuropathol Commun ; 7(1): 219, 2019 12 23.
Article in English | MEDLINE | ID: mdl-31870437

ABSTRACT

Synucleinopathies are mostly sporadic neurodegenerative disorders of partly unexplained aetiology, and include Parkinson's disease (PD) and multiple system atrophy (MSA). We have further investigated our recent finding of somatic SNCA (α-synuclein) copy number variants (CNVs, specifically gains) in synucleinopathies, using Fluorescent in-situ Hybridisation for SNCA, and single-cell whole genome sequencing for the first time in a synucleinopathy. In the cingulate cortex, mosaicism levels for SNCA gains were higher in MSA and PD than controls in neurons (> 2% in both diseases), and for MSA also in non-neurons. In MSA substantia nigra (SN), we noted SNCA gains in > 3% of dopaminergic (DA) neurons (identified by neuromelanin) and neuromelanin-negative cells, including olig2-positive oligodendroglia. Cells with CNVs were more likely to have α-synuclein inclusions, in a pattern corresponding to cell categories mostly relevant to the disease: DA neurons in Lewy-body cases, and other cells in the striatonigral degeneration-dominant MSA variant (MSA-SND). Higher mosaicism levels in SN neuromelanin-negative cells may correlate with younger onset in typical MSA-SND, and in cingulate neurons with younger death in PD. Larger sample sizes will, however, be required to confirm these putative findings. We obtained genome-wide somatic CNV profiles from 169 cells from the substantia nigra of two MSA cases, and pons and putamen of one. These showed somatic CNVs in ~ 30% of cells, with clonality and origins in segmental duplications for some. CNVs had distinct profiles based on cell type, with neurons having a mix of gains and losses, and other cells having almost exclusively gains, although control data sets will be required to determine possible disease relevance. We propose that somatic SNCA CNVs may contribute to the aetiology and pathogenesis of synucleinopathies, and that genome-wide somatic CNVs in MSA brain merit further study.


Subject(s)
Brain/metabolism , DNA Copy Number Variations , Multiple System Atrophy/genetics , Parkinson Disease/genetics , alpha-Synuclein/genetics , Gyrus Cinguli/metabolism , Humans , Male , Neurons/metabolism , Single-Cell Analysis
17.
Environ Sci Process Impacts ; 21(12): 2128-2140, 2019 Dec 11.
Article in English | MEDLINE | ID: mdl-31681920

ABSTRACT

Determining inorganic nutrient profiles to support understanding of nitrogen transformations in stream sediments is challenging, due to nitrification and denitrification being confined to particular conditions in potentially heterogeneous sediment influenced by benthic microalgae, rooted aquatic plants and/or diel light cycles. The diffusive gradients in thin films (DGT) and diffusive equilibration in thin films (DET) techniques allow in situ determination of porewater concentration profiles, and distributions for some solutes. In this study, DGT, DET and conventional porewater extraction (sectioning and centrifugation) methods were compared for ammonium and nitrate in stream sediments under light and dark conditions. Two-dimensional distributions of Fe(ii) and PO4-P were also provided to indicate the degree of spatial and temporal heterogeneity in sediment porewater, which can explain the sources and sinks of ammonium at various depths in the sediments. Although the conventional porewater extraction method consistently measured higher NH4-N concentrations than the DGT and DET techniques, the study showed that the DET measurements were the most reliable indicator of porewater NH4-N concentrations, with the DGT data being usefully supplementary. However, a large proportion of the NO3-N concentrations measured by DGT and DET were close to or below the method detection limits. Therefore, further development of these techniques is required to reduce the blanks and detection limits to allow natural low sediment porewater NO3-N concentrations to be accurately monitored using DGT and DET. The study indicated that benthic microalgae had direct and indirect influences on porewater nutrient distributions over light-dark cycles. Overall, DGT and DET techniques can be useful for monitoring porewater nutrient concentrations and profiles and for determining how biological processes drive changes in sediment nutrient concentrations and distributions.


Subject(s)
Environmental Monitoring/methods , Geologic Sediments/chemistry , Rivers/chemistry , Water Cycle , Water Pollutants, Chemical/analysis , Ammonia/analysis , Diffusion , Nitrates/analysis
19.
JMIR Public Health Surveill ; 5(3): e12233, 2019 08 04.
Article in English | MEDLINE | ID: mdl-31418425

ABSTRACT

BACKGROUND: Annually, there are approximately 25 million unsafe abortions, and this remains a leading cause of maternal morbidity and mortality. In settings where abortion is restricted, women are increasingly able to self-manage abortions by purchasing abortion medications such as misoprostol and mifepristone (RU-486) from pharmacies or other drug sellers. Better availability of these drugs has been shown to be associated with reductions in complications from unsafe abortions. In Bangladesh, abortion is restricted; however, menstrual regulation (MR) was introduced in the 1970s as an interim method of preventing pregnancy. Pharmacy provision of medications for MR is widespread, but customers purchasing these drugs from pharmacies often do not have access to quality information on dosage and potential complications. OBJECTIVE: This study aimed to describe a call center intervention in Bangladesh, and assess call center use over time and how this changed when a new MR product (combined mifepristone-misoprostol) was introduced into the market. METHODS: In 2010, Marie Stopes Bangladesh established a care provider-assisted call center to reduce potential harm from self-administration of MR medications. The call center number was advertised widely in pharmacies and on MR product packaging. We conducted a secondary analysis of routine data collected by call center workers between July 2012 and August 2016. We investigated the reported types of callers, the reason for call, and reported usage of MR products before and after November 2014. We used an interrupted time series (ITS) analysis to formally assess levels of change in caller characteristics and reasons for calling. RESULTS: Over the 4-year period, 287,095 calls about MR were received and the number of users steadily increased over time. The most common callers (of 287,042 callers) were MR users (67,438, 23.49%), their husbands (65,999, 22.99%), pharmacy workers (65,828, 22.93%), and village doctors (56,036, 19.52%). Most MR calls were about misoprostol, but after November 2014, a growing proportion of calls were about the mifepristone-misoprostol regimen. The most common reasons (of 287,042 reasons) for calling were to obtain information about the regimen (208,605, 72.66%), to obtain information about side effects (208,267, 72.54%), or to report side effects (49,930, 17.39%). The ITS analyses showed that after November 2014, an increasing number of calls were from MR users who had taken the complete regimen (P=.02 and who were calling to discuss reported side effects (P=.01) and pain medication (P=.01), and there were fewer calls asking about dosages (P<.001). CONCLUSIONS: The high call volume suggests that this call center intervention addressed an unmet demand for information about MR medications from both MR users and health care providers. Call center interventions may improve the quality of information available by providing information directly to MR users and drug sellers, and thus reducing the potential harm from self-management of MR medications.

20.
Sci Total Environ ; 636: 1416-1427, 2018 Sep 15.
Article in English | MEDLINE | ID: mdl-29913602

ABSTRACT

Sediments delivered to freshwater and marine environments can make important contributions to the aquatic bioavailable nutrient pool. In the Great Barrier Reef (GBR) catchments, particulate nutrients comprise an important fraction of the end of catchment loads; however, their contribution to the bioavailable nutrient pool is not well understood. This research determined which particulate nutrient parameters are the best indicators of the potential effect of fine sediment (<10 µm) on phytoplankton growth. Surface and subsurface sediments were lab-generated to cover a wide spectrum of particulate nutrient bioavailability from key soil types, land uses and erosion processes (hillslope and gully) in a wet and a dry tropics catchment of the GBR. Phytoplankton bioassays were used to assess freshwater and marine phytoplankton responses to sediments. The best indicators were selected by regressing measurements of phytoplankton growth against nutrient bioavailability parameters measured on the sediments. The selected indicator equations included organic carbon (C) pools for both fresh and marine water, highlighting the role of bacteria in mediating nutrient availability for phytoplankton. The equations also included various fractions of particulate nitrogen (N) (differentiating the adsorbed ammonium-N from the particulate organic N), and the ratios of C to N, which indicate the lability of the organic matter present in the sediment. Dissolved reactive phosphorus was also an important indicator in freshwater. The indicators performed better in assessing bioavailability potential than traditional methods to monitor particulate nutrients, e.g., particulate N and particulate phosphorus. Phytoplankton bioassays indicated that nutrients in sediment can promote phytoplankton growth, with nutrient bioavailability depending not only on sediment load, but also sediment characteristics associated with its parent soil. These characteristics vary with soil type, land use and erosion process. Findings will help prioritize erosion control to catchment areas which are most likely to contribute large amounts of bioavailable particulate nutrients to the GBR.


Subject(s)
Coral Reefs , Environmental Monitoring , Nitrogen/analysis , Phosphorus/analysis , Phytoplankton/physiology , Animals , Anthozoa , Australia , Ecosystem , Fresh Water , Seawater
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