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1.
Metabolomics ; 17(10): 90, 2021 09 23.
Artículo en Inglés | MEDLINE | ID: mdl-34557980

RESUMEN

INTRODUCTION: Poor gestational outcomes due to placental insufficiency can have lifelong consequences for mother and child. OBJECTIVE: There is a need for better methods of diagnosis, and elemental metabolomics may provide a means to determine the risk of gestational disorders. METHODS: This study used blood plasma samples collected at 36 weeks' gestation from women who later developed preeclampsia (n = 38), or small-for-gestational age babies (n = 91), along with matched controls (n = 193). Multi-element analysis was conducted by inductively coupled plasma mass spectrometer (ICP-MS), allowing simultaneous measurement of 28 elements. RESULTS: Women who later developed PE, exhibited significantly increased concentrations of K, Rb and Ba. For SGA pregnancies, there was a significant increase in Cu and a decrease in As concentrations. Despite significant differences in single elements, the elemental profile of groups indicated no clustering of control, PE, or SGA samples. Positive predicative values correctly identified approximately 60% of SGA and 70% of PE samples. CONCLUSION: This is the first-time elemental metabolomics has been used to predict SGA and PE at 36 weeks. Though significant changes were identified, routine clinical use may be limited but may contribute to a multi marker test. Future analysis should include other biomarkers, metabolic data or clinical measurements made throughout gestation.


Asunto(s)
Preeclampsia , Oligoelementos , Biomarcadores , Niño , Femenino , Edad Gestacional , Humanos , Recién Nacido , Recién Nacido Pequeño para la Edad Gestacional , Placenta , Preeclampsia/diagnóstico , Embarazo
2.
Environ Sci Technol ; 55(17): 11848-11858, 2021 09 07.
Artículo en Inglés | MEDLINE | ID: mdl-34382781

RESUMEN

Synchrotron-based X-ray fluorescence microscopy (XFM) coupled with X-ray absorption near-edge structure (XANES) imaging was used to study selenium (Se) biodistribution and speciation in Limnodynastes peronii tadpoles. Tadpoles were exposed to dissolved Se (30 µg/L) as selenite (SeIV) or selenate (SeVI) for 7 days followed by 3 days of depuration. High-resolution elemental maps revealed that Se partitioned primarily in the eyes (specifically the eye lens, iris, and retinal pigmented epithelium), digestive and excretory organs of SeIV-exposed tadpoles. Speciation analysis confirmed that the majority of accumulated Se was converted to organo-Se. Multielement analyses provided new information on Se colocalization and its impact on trace element homeostasis. New insights into the fate of Se on a whole organism scale contribute to our understanding of the mechanisms and risks associated with Se pollution.


Asunto(s)
Compuestos de Selenio , Selenio , Animales , Larva , Ácido Selénico , Sincrotrones , Distribución Tisular , Humedales
3.
Environ Sci Technol ; 52(3): 1118-1127, 2018 02 06.
Artículo en Inglés | MEDLINE | ID: mdl-29303570

RESUMEN

Antimony (Sb) and arsenic (As) are priority environmental contaminants that often co-occur at mining-impacted sites. Despite their chemical similarities, Sb mobility in waterlogged sediments is poorly understood in comparison to As, particularly across the sediment-water interface (SWI) where changes can occur at the millimeter scale. Combined diffusive gradients in thin films (DGT) and diffusive equilibration in thin films (DET) techniques provided a high resolution, in situ comparison between Sb, As, and iron (Fe) speciation and mobility across the SWI in contaminated freshwater wetland sediment mesocosms under an oxic-anoxic-oxic transition. The shift to anoxic conditions released Fe(II), As(III), and As(V) from the sediment to the water column, consistent with As release being coupled to the reductive dissolution of iron(III) (hydr)oxides. Conversely, Sb(III) and Sb(V) effluxed to the water column under oxic conditions and fluxed into the sediment under anoxic conditions. Porewater DGT-DET depth profiles showed apparent decoupling between Fe(II) and Sb release, as Sb was primarily mobilized across the SWI under oxic conditions. Solid-phase X-ray absorption spectroscopy (XAS) revealed the presence of an Sb(III)-S phase in the sediment that increased in proportion with depth and the transition from oxic to anoxic conditions. The results of this study showed that Sb mobilization was decoupled from the Fe cycle and was, therefore, more likely linked to sulfur and/or organic carbon (e.g., most likely authigenic antimony sulfide formation or Sb(III) complexation by reduced organic sulfur functional groups).


Asunto(s)
Arsénico , Antimonio , Compuestos Férricos , Sedimentos Geológicos , Humedales
4.
Environ Sci Technol ; 50(24): 13446-13454, 2016 12 20.
Artículo en Inglés | MEDLINE | ID: mdl-27993039

RESUMEN

Nutrient concentrations in freshwater are highly variable over time, with changes driven by weather events, anthropogenic sources, modifications to catchment hydrology or habitats, and internal biogeochemical processes. Measuring infrequently collected grab samples is unlikely to adequately represent nutrient concentrations in such dynamic systems. In contrast, in situ passive sampling techniques, such as the "diffusive gradients in thin films" (DGT) technique, provide time-weighted average analyte concentrations over the entire deployment time. A pair of recently developed DGT techniques for nitrate (A520E-DGT) and ammonium (PrCH-DGT), as well as the Metsorb-DGT technique for phosphate, were used to monitor inorganic nutrients in different freshwater systems (i.e., streams and wetlands) with a range of environmental values and that were affected by different catchment types. Measurements of grab samples collected frequently (1-2 times daily, 8-10 a.m. and 2-4 p.m.) showed that concentrations of NH4-N and NO3-N changed dramatically in most of the studied freshwater systems over short time scales, while there were only relatively small fluctuations in PO4-P. The DGT measurements were highly representative in comparison with the average nutrient concentrations obtained from daily grab samples over short-term (24 h) and long-term (72 h) deployments. The ratios of DGT-labile concentrations to the average concentrations from grab samples were between 1.00 and 1.12 over the studied deployment periods. The results of this study confirmed that DGT measurements provided a reliable and robust method for monitoring NH4-N, NO3-N, and PO4-P in a diverse range of dynamic freshwater systems.


Asunto(s)
Monitoreo del Ambiente , Agua Dulce , Difusión , Nitratos , Tiempo (Meteorología)
5.
Environ Microbiol ; 16(8): 2458-74, 2014 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-24428563

RESUMEN

Modern microbial mats are highly complex and dynamic ecosystems. Diffusive equilibration in thin films (DET) and diffusive gradients in thin films (DGT) samplers were deployed in a modern smooth microbial mat from Shark Bay in order to observe, for the first time, two-dimensional distributions of porewater solutes during day and night time. Two-dimensional sulfide and alkalinity distributions revealed a strong spatial heterogeneity and a minor contribution of sulfide to alkalinity. Phosphate distributions were also very heterogeneous, while iron(II) distributions were quite similar during day and night with a few hotspots of mobilization. Lipid biomarkers from the three successive layers of the mat were also analysed in order to characterize the microbial communities regulating analyte distributions. The major hydrocarbon products detected in all layers included n-alkanes and isoprenoids, whilst other important biomarkers included hopanoids. Phospholipid fatty acid profiles revealed a decrease in cyanobacterial markers with depth, whereas sulfate-reducing bacteria markers increased in abundance in accordance with rising sulfide concentrations with depth. Despite the general depth trends in community structure and physiochemical conditions within the mat, two-dimensional solute distributions showed considerable small-scale lateral variability, indicating that the distributions and activities of the microbial communities regulating these solute distributions were equally heterogeneous and complex.


Asunto(s)
Bahías/microbiología , Cianobacterias/metabolismo , Sedimentos Geológicos/microbiología , Consorcios Microbianos/fisiología , Bacterias Reductoras del Azufre/metabolismo , Biomarcadores/metabolismo , Difusión , Ecosistema , Hidrocarburos/aislamiento & purificación , Hidrocarburos/metabolismo , Concentración de Iones de Hidrógeno , Lípidos/química , Sulfuros/metabolismo
6.
Anal Chem ; 86(1): 427-34, 2014 Jan 07.
Artículo en Inglés | MEDLINE | ID: mdl-24251902

RESUMEN

A new diffusive gradients in thin films (DGT) technique with a mixed binding layer (Chelex-100 and the titanium dioxide based adsorbent Metsorb) is described for the simultaneous measurement of labile trace metal (Mn, Co, Ni, Cu, Cd, and Pb) and oxyanion (V, As, Mo, Sb, W, and P) concentrations in freshwater and seawater. The mixed binding layer (MBL) DGT technique was evaluated against the Chelex-DGT and Metsorb-DGT techniques, and all elution efficiencies and diffusion coefficients have been remeasured for the above analytes. Diffusion coefficients (D) measured using MBL-DGT generally agreed well with those measured by Chelex-DGT (DMBL/DChelex = 0.97-1.05), Metsorb-DGT (DMBL/DMetsorb = 0.97-1.01), and diffusion cell experiments. The measurement of trace metals and oxyanions by MBL-DGT was independent of pH (5.03-8.05) and ionic strength (I = 0.001-0.7 mol L(-1)). MBL-DGT accurately measured the concentration of trace metals and oxyanions in synthetic freshwater (CMBL/CSol = 0.82-1.18) over the 4 day deployment and also agreed well with Metsorb-DGT (CMBL/CMetsorb = 0.84-0.94) and Chelex-DGT (CMBL/CChelex = 0.88-1.11) measurements. In synthetic seawater, MBL-DGT accurately measured the concentration of metals and oxyanions (CMBL/CSol = 0.85-1.12) over 4 days, with the exception of Mo-none of the DGT techniques were capable of measuring Mo in seawater. MBL-DGT measured the Mn concentration accurately over the entire 4 day period, whereas Chelex-DGT only measured Mn accurately up to 2 days. The MBL-DGT method described in this study offers significant advantages over the ferrihydrite-Chelex-DGT method reported previously. These advantages include the commercial availability of both Metsorb and Chelex-100, the higher accuracy of Metsorb for measuring some oxyanions in freshwater and seawater, and the possibility of measuring Fe, which would not be possible using the Chelex-ferrihydrite binding layer.

8.
Mar Pollut Bull ; 201: 116217, 2024 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-38520999

RESUMEN

Satellite retrieval of total suspended solids (TSS) and chlorophyll-a (chl-a) was performed for the Gold Coast Broadwater, a micro-tidal estuarine lagoon draining a highly developed urban catchment area with complex and competing land uses. Due to the different water quality properties of the rivers and creeks draining into the Broadwater, sampling sites were grouped in clusters, with cluster-specific empirical/semi-empirical prediction models developed and validated with a leave-one-out cross validation approach for robustness. For unsampled locations, a weighted-average approach, based on their proximity to sampled sites, was developed. Confidence intervals were also generated, with a bootstrapping approach and visualised through maps. Models yielded varying accuracies (R2 = 0.40-0.75). Results show that, for the most significant poor water quality event in the dataset, caused by summer rainfall events, elevated TSS concentrations originated in the northern rivers, slowly spreading southward. Conversely, high chl-a concentrations were first recorded in the southernmost regions of the Broadwater.


Asunto(s)
Clorofila , Monitoreo del Ambiente , Australia , Clorofila/análisis , Clorofila A , Monitoreo del Ambiente/métodos , Calidad del Agua
9.
Aquat Toxicol ; 255: 106394, 2023 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-36603369

RESUMEN

Cell-based toxicity testing has emerged as a useful tool in (eco)toxicological research, allowing the ethical assessment of the effects of contaminants such as trace metals on marine megafauna. However, metal interactions with various dissolved ligands in the microplate environment may influence the effective exposure concentrations. Hence, the cells are not exposed to the nominal concentrations within the test system. This study aimed to establish and evaluate the effectiveness of cell-based bioassays for investigating the toxicity of selected metals in dugongs through the following objectives: (1) measure the cytotoxic potential of cadmium (Cd2+), and chromium (Cr6+) to dugong skin cell cultures, (2) investigate the interactions between media constituents and selected trace metals in cell-based bioassays, and (3) evaluate the risk to a free-ranging population of dugong based on effect values. Chromium was the most toxic of the metals tested (EC50 = 1.14 µM), followed by Cd (EC50 = 6.35 µM). Assessment of ultrafiltered (< 3 kDa) exposure media showed that 1% and 92.5% of Cr and Cd were associated with larger organic components of the media. Further, the binding of Cd to media constituents was calculated to underestimate Cd toxicity in cell-based assays by an order of magnitude. This understanding of metal partitioning in cell-based bioassays provides a more accurate method for assessing toxicity in cell-based bioassays. In addition, this study illustrated that dugong cells are more sensitive to Cr and Cd than other marine wildlife species. The chemical risk assessment found the dugong population in Moreton Bay to be at high risk from Cd exposure.


Asunto(s)
Dugong , Oligoelementos , Contaminantes Químicos del Agua , Animales , Dugong/metabolismo , Cadmio/toxicidad , Cadmio/metabolismo , Contaminantes Químicos del Agua/toxicidad , Metales/metabolismo , Cromo , Oligoelementos/metabolismo , Bioensayo
10.
Environ Sci Technol ; 46(4): 2267-75, 2012 Feb 21.
Artículo en Inglés | MEDLINE | ID: mdl-22268706

RESUMEN

Aluminum is acutely toxic, and elevated concentrations of dissolved Al can have detrimental effects on both terrestrial and aquatic ecosystems. Robust analytical methods that can determine environmentally relevant Al fractions accurately and efficiently are required by the environmental monitoring community. A simple, robust passive sampling method, the diffusive gradients in thin films (DGT) technique, was evaluated for the measurement of dissolved Al species in freshwater and marine water using either Chelex-100 or Metsorb (a titanium dioxide-based binding agent) as the adsorbent. Mass vs time DGT deployments at pH 5.05 (Al(3+) and Al(OH)(2+) dominate) and 8.35 (Al(OH)(4)(-) dominates) demonstrated linear uptake of Al (R(2) = 0.989 and 0.988, respectively) for Metsorb. Similar deployments of Chelex-DGT showed linear uptake at pH 5.05 (R(2) = 0.994); however, at pH 8.35 the mass of Al accumulated was 40-70% lower than predicted, suggesting that Chelex-100 is not suitable for Al measurements at high pH. The Metsorb-DGT measurement was independent of pH (5.0-8.5) and ionic strength (0.001-0.7 mol L(-1) NaNO(3)), whereas the Chelex-DGT measurement was only independent of ionic strength at pH 5.0. At pH 8.4, increasing ionic strength led to considerable underestimation (up to 67%) of Al concentration. Deployments of Metsorb-DGT (up to 4 days) in synthetic freshwater (pH range 5.4-8.1) and synthetic seawater (pH 8.15) resulted in linear mass uptakes, and the concentration measured by DGT agreed well with solution concentrations. Conversely, deployment of Chelex-DGT in synthetic seawater and freshwater (pH ≥7.7 Al(OH)(4)(-) dominant species) resulted in a decrease in accumulated mass with increasing deployment time. In situ field evaluations in fresh, estuarine, and marine waters confirmed that Metsorb-DGT was more accurate than Chelex-DGT for the measurement of dissolved Al in typical environmental waters.


Asunto(s)
Aluminio/análisis , Monitoreo del Ambiente/métodos , Resinas Sintéticas/química , Titanio/química , Contaminantes Químicos del Agua/análisis , Adsorción , Aluminio/química , Quelantes/química , Agua Dulce/análisis , Concentración de Iones de Hidrógeno , Concentración Osmolar , Agua de Mar/análisis , Contaminantes Químicos del Agua/química
11.
Environ Sci Technol ; 46(7): 3981-9, 2012 Apr 03.
Artículo en Inglés | MEDLINE | ID: mdl-22397626

RESUMEN

Mobilization of arsenic from freshwater and estuarine sediments during the transition from oxic to anoxic conditions was investigated using recently developed diffusive sampling techniques. Arsenic speciation and Fe(II) concentrations were measured at high resolution (1-3 mm) with in situ diffusive gradients in thin films (DGT) and diffusive equilibration in thin films (DET) techniques. Water column anoxia induced Fe(II) and As(III) fluxes from the sediment. A correlation between water column Fe(II) and As(III) concentrations was observed in both freshwater (r(s) = 0.896, p < 0.001) and estuarine (r(s) = 0.557, p < 0.001) mesocosms. Porewater sampling by DGT and DET techniques confirmed that arsenic mobilization was associated with the reductive dissolution of Fe(III) (hydr)oxides in the suboxic zone of the sediment; a relationship that was visible because of the ability to measure the coincident profiles of these species using combined DGT and DET samplers. The selective measurement of As(III) and total inorganic arsenic by separate DGT samplers indicated that As(III) was the primary species mobilized from the solid phase to the porewater. This measurement approach effectively ruled out substantial As(V) mobilization from the freshwater and estuarine sediments in this experiment. This study demonstrates the capabilities of the DGT and DET techniques for investigating arsenic speciation and mobilization over a range of sediment conditions.


Asunto(s)
Arsénico/aislamiento & purificación , Monitoreo del Ambiente/métodos , Sedimentos Geológicos/química , Movimiento (Física) , Oxígeno/química , Arsénico/química , Difusión , Hierro/química , Porosidad , Solubilidad , Agua/química
12.
Mar Pollut Bull ; 185(Pt A): 114234, 2022 Dec.
Artículo en Inglés | MEDLINE | ID: mdl-36257244

RESUMEN

This study establishes baseline water quality characteristics for the Gold Coast Broadwater, southern Moreton Bay (Australia) utilising routinely monitored parameters between 2016 and 2021, across 18 sites. Combined site mean concentrations of NOx-N, NH3-N and total nitrogen were 11.4 ± 33.4 µg/L, 12.7 ± 27.2 µg/L, and 169 ± 109 µg/L, respectively, whilst PO4-P and total phosphorous were 7.30 ± 5.10 µg/L and 21.7 ± 14.1 µg/L. Additionally, total suspended solids and turbidity combined site means were 6.6 ± 6.0 mg/L and 3.4 ± 2.9 NTU, respectively. During high rainfall periods nutrient concentrations increased by up to >200-, >150-, 15-, 12- and >12-fold for NOx-N, NH3-N, TN, PO4-P and TP, respectively, compared to quiescent conditions. Furthermore, TSS and NTU values increased by up to 15- and 40-fold during periods of measured rainfall compared to quiescent conditions.


Asunto(s)
Contaminantes Químicos del Agua , Calidad del Agua , Bahías , Monitoreo del Ambiente , Nitrógeno/análisis , Fósforo/análisis , Contaminantes Químicos del Agua/análisis
13.
Anal Chem ; 83(21): 8293-9, 2011 Nov 01.
Artículo en Inglés | MEDLINE | ID: mdl-21967720

RESUMEN

A diffusive gradients in thin films (DGT) technique for selectively measuring As(III) utilizes commercially available 3-mercaptopropyl-functionalized silica gel. Deployment of the new technique alongside the Metsorb-DGT for total inorganic arsenic allows the calculation of As(III) directly and As(V) by difference. Uptake of As(III) by mercapto-silica was quantitative and elution with a mixture of 1 mol L(-1) HNO(3) and 0.01 mol L(-1) KIO(3) gave a recovery of 85.6 ± 1.7%. DGT validation experiments showed linear accumulation of As(III) over time (R(2) > 0.998). Accumulation was unaffected by varying ionic strength (0.0001-0.75 mol L(-1) NaNO(3)) and pH (3.5-8.5). Deployment of mercapto-silica DGT and Metsorb DGT in seawater spiked with As(III) and As(V) demonstrated the ability of the combined approach to accurately quantify both species in the presence of potential competing ions. Ferrihydrite DGT, which has been previously reported for the measurement of total inorganic arsenic, was evaluated in seawater and shown to underestimate both As(III) and As(V) at longer deployment times (72 h). Reproducibility of the new mercapto-silica DGT technique was good (relative standard deviations < 9%), and the average method detection limit was sufficiently low to allow quantification of ultratrace concentrations of As(III) (0.03 µg L(-1); 72 h deployment).


Asunto(s)
Arsénico/análisis , Monitoreo del Ambiente , Propanoles/química , Agua de Mar/análisis , Gel de Sílice/química , Compuestos de Sulfhidrilo/química , Difusión , Compuestos Férricos/química , Concentración de Iones de Hidrógeno , Concentración Osmolar , Reproducibilidad de los Resultados
14.
Biol Trace Elem Res ; 199(1): 26-40, 2021 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-32239374

RESUMEN

A normal pregnancy is essential to establishing a healthy start to life. Complications during have been associated with adverse perinatal outcomes and lifelong health problems. The ability to identify risk factors associated with pregnancy complications early in gestation is vitally important for preventing negative foetal outcomes. Maternal nutrition has been long considered vital to a healthy pregnancy, with micronutrients and trace elements heavily implicated in maternofoetal metabolism. This study proposed the use of elemental metabolomics to study multiple elements at 18 weeks gestation from blood plasma and urine to construct models that could predict outcomes such as small for gestational age (SGA) (n = 10), low placental weight (n = 18), and preterm birth (n = 13) from control samples (n = 87). Samples collected from the Lyell McEwin Hospital in Adelaide, South Australia, were measured for 27 plasma elements and 37 urine elements by inductively coupled plasma mass spectrometry. Exploratory analysis indicated an average selenium concentration 20 µg/L lower than established reference ranges across all groups, low zinc in preterm (0.64 µg/L, reference range 0.66-1.10 µg/L), and higher iodine in preterm and SGA gestations (preterm 102 µg/L, SGA 111 µg/L, reference range 40-92 µg/L). Using random forest algorithms with receiver operating characteristic curves, low placental weight was predicted with 86.7% accuracy using plasma, 78.6% prediction for SGA with urine, and 73.5% determination of preterm pregnancies. This study indicates that elemental metabolomic modelling could provide a means of early detection of at-risk pregnancies allowing for more targeted monitoring of mothers, with potential for early intervention strategies to be developed.


Asunto(s)
Nacimiento Prematuro , Femenino , Humanos , Recién Nacido , Metabolómica , Placenta , Plasma , Embarazo , Resultado del Embarazo
15.
Water Res ; 209: 117967, 2021 Dec 15.
Artículo en Inglés | MEDLINE | ID: mdl-34936976

RESUMEN

Stormwater runoff typically contains significant quantities of metal contaminants that enter urban waterways over short durations and represent a potential risk to water quality. The origin of metals within the catchment and processes that occur over the storm can control the partitioning of metals between a range of different forms. Understanding the fraction of metals present in a form that is potentially bioavailable to aquatic organisms is useful for environmental risk assessment. To help provide this information, the forms and dynamics of metal contaminants in an urban system were assessed across a storm. Temporal patterns in the concentration of metals in dissolved and particulate (total suspended solids; TSS) forms were assessed from water samples, and diffusive gradients in thin-films (DGTs) were deployed to measure the DGT-labile time-integrated metal concentration. Results indicate that the concentrations of dissolved and TSS-associated metals increased during the storm, with the metals Al, Cd, Co, Cu, Pb and Zn representing the greatest concern relative to water quality guideline values (GVs). The portion of labile metal as measured by DGT devices indicated that during the storm a substantial fraction (∼98%) of metals were complexed and pose a lower risk of acute toxicity to aquatic organisms. Comparison of DGT results to GVs indicate that current GVs are likely quite conservative when assessing stormwater pollution risks with regards to metal contaminants. This study provides valuable insight into the forms and dynamics of metals in an urban system receiving stormwater inputs and assists with the development of improved approaches for the assessment of short-term, intermittent discharge events.

16.
Anal Chem ; 82(17): 7401-7, 2010 Sep 01.
Artículo en Inglés | MEDLINE | ID: mdl-20695441

RESUMEN

A new diffusive gradients in a thin film (DGT) technique, using a titanium dioxide based adsorbent (Metsorb), has been developed and evaluated for the determination of dissolved inorganic arsenic and selenium. As(III), As(V), and Se(IV) were found to be quantitatively accumulated by the adsorbent (uptake efficiencies of 96.5-100%) and eluted in 1 M NaOH (elution efficiencies of 81.2%, 75.2%, and 88.7%). Se(VI) was not quantitatively accumulated by the adsorbent (<20%). Laboratory DGT validation experiments gave linear mass uptake over time (R(2) >or= 0.998) for As(III), As(V), and Se(IV). Consistent uptake occurred over pH (3.5-8.5) and ionic strength (0.0001-0.75 mol L(-1) NaNO(3)) ranges typical of natural waters, including seawater. Field deployments of DGT probes with various diffusive layer thicknesses confirmed the use of the technique in situ, allowing calculation of the diffusive boundary layers and an accurate measurement of inorganic arsenic. Reproducibility of the technique in field deployments was good (relative standard deviation <8%). Limits of detection (4 day deployments) were 0.01 microg L(-1) for inorganic arsenic and 0.05 microg L(-1) for Se(IV). The results of this study confirmed that DGT with Metsorb was a reliable and robust method for the measurement of inorganic arsenic and the selective measurement of Se(IV) within useful limits of accuracy.


Asunto(s)
Arsénico/análisis , Selenio/análisis , Titanio/química , Adsorción , Difusión , Agua Dulce/química , Concentración de Iones de Hidrógeno , Concentración Osmolar , Agua de Mar/química
17.
Environ Sci Technol ; 44(24): 9419-24, 2010 Dec 15.
Artículo en Inglés | MEDLINE | ID: mdl-21090745

RESUMEN

A new diffusive gradients in a thin film (DGT) technique for measuring dissolved reactive phosphorus (DRP) in fresh and marine waters is reported. The new method, which uses a commercially available titanium dioxide based adsorbent (Metsorb), was evaluated and compared to the well-established ferrihydrite-DGT method (ferrihydrite cast within the polyacrylamide gel). DGT time-series experiments showed that the mass of DRP accumulated by Metsorb and ferrihydrite was linear with time when deployed in simple solutions. Both DGT methods showed predictable uptake across the pH (4.0-8.3) and ionic strength (0.0001-1 mol L(-1) NaNO(3)) ranges investigated, and the total capacity of the Metsorb binding phase (∼40,000 ng P) was 2.5-5 times higher than the reported total capacity of the ferrihydrite binding phase. The measurement of DRP in synthetic freshwater and synthetic seawater by Metsorb-DGT over a 4 day deployment period showed excellent agreement with the concentration of DRP measured directly in solution, whereas the ferrihydrite-DGT method significantly underestimated (23-30%) the DRP concentration in synthetic seawater for deployment times of two days or more. Field deployments of Metsorb-DGT samplers with various diffusive layer thicknesses allowed accurate measurement of both the diffusive boundary layer thickness and DRP concentration in situ. The Metsorb-DGT method performs similarly to ferrihydrite-DGT for freshwater measurements but is shown to be more accurate than the ferrihydrite method for determining DRP in seawater.


Asunto(s)
Monitoreo del Ambiente/métodos , Fósforo/análisis , Titanio/química , Contaminantes Químicos del Agua/análisis , Agua Dulce/química , Concentración de Iones de Hidrógeno , Concentración Osmolar , Fósforo/química , Agua de Mar/química , Contaminantes Químicos del Agua/química
18.
Chemosphere ; 244: 125388, 2020 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-31809928

RESUMEN

Measurement of sulfide in pore waters is critical for understanding biogeochemical processes, especially within coastal sediments. Here we report the development of a new colorimetric DET (diffusive equilibration in thin films) technique for determining mm-resolution, two-dimensional sulfide distributions in sediment pore waters. This colorimetric sulfide DET method was based on the standard spectrophotometric methylene blue assay, but modified to allow quantitation of sulfide by computer imaging densitometry. The method detection and effective upper measurement limits of the optimised technique were 3.7 and 1000 µmol L-1, respectively. The optimised sulfide DET method was combined with the colorimetric iron(II) DET method to obtain co-distributions in coastal seagrass (Zostera muelleri) colonised sediment under light and dark conditions. In the dark, seagrass sediments were more reduced than in the light, with large areas being dominated by high porewater sulfide concentrations. These co-distributions were compared with those obtained using the previously described DET-DGT (diffusive gradients in thin films) method for measuring iron(II) and sulfide co-distributions. There was less overlap of iron(II) and sulfide distributions using the sulfide DET as the two DET methods are influenced most by the later hours of deployment, whereas the sulfide-DGT measurement integrates concentrations over the whole deployment period. Overlap was most apparent in very dynamic sediment zones, such as burrow wall sediments.


Asunto(s)
Monitoreo del Ambiente/métodos , Sulfuros/análisis , Contaminantes Químicos del Agua/análisis , Colorimetría , DEET , Difusión , Compuestos Ferrosos/análisis , Sedimentos Geológicos , Hierro/química , Zosteraceae
19.
J Trace Elem Med Biol ; 59: 126419, 2020 May.
Artículo en Inglés | MEDLINE | ID: mdl-31711786

RESUMEN

BACKGROUND: Trace elements are an essential requirement for human health and development and changes in trace element status have been associated with pregnancy complications such as gestational diabetes mellitus (GDM), pre-eclampsia (PE), fetal growth restriction (FGR), and preterm birth. Elemental metabolomics, which involves the simultaneous quantification and characterisation of multiple elements, could provide important insights into these gestational disorders. METHODS: This study used an Agilent 7900 inductively coupled plasma mass spectrometer (ICP-MS) to simultaneously measure 68 elements, in 166 placental cord blood samples collected from women with various pregnancy complications (control, hypertensive, PE, GDM, FGR, pre-term, and post-term birth). RESULTS: There were single element differences across gestational outcomes for elements Mg, P, Cr, Ni, Sr, Mo, I, Au, Pb, and U. Hypertensive and post-term pregnancies were significantly higher in Ni concentrations when compared to controls (control = 2.74 µg/L, hypertensive = 6.72 µg/L, post-term = 7.93 µg/L, p < 0.05), iodine concentration was significantly higher in post-term pregnancies (p < 0.05), and Pb concentrations were the lowest in pre-term pregnancies (pre-term = 2.79 µg/L, control = 4.68 µg/L, PE = 5.32 µg/L, GDM = 8.27 µg/L, p < 0.01). Further analysis was conducted using receiver operating characteristic (ROC) curves for differentiating pregnancy groups. The ratio of Sn/Pb showed the best diagnostic power in discriminating between control and pre-term birth with area under the curve (AUC) 0.86. When comparing control and post-term birth, Mg/Cr (AUC = 0.84), and Cr (AUC = 0.83) had the best diagnostic powers. In pre-term and post-term comparisons Ba was the best single element (81.5%), and P/Cu provided the best ratio (91.7%). CONCLUSIONS: This study has shown that analysis of multiple elements can enable differentiation between fetal cord blood samples from control, hypertensive, PE, GDM, FGR, pre and post-term pregnancies. This data highlights the power of elemental metabolomics and provides a basis for future gestational studies.


Asunto(s)
Sangre Fetal/química , Metabolómica , Oligoelementos/sangre , Oligoelementos/metabolismo , Adulto , Femenino , Sangre Fetal/metabolismo , Humanos , Masculino , Embarazo , Adulto Joven
20.
Sci Total Environ ; 740: 140042, 2020 Oct 20.
Artículo en Inglés | MEDLINE | ID: mdl-32927538

RESUMEN

There is increasing interest in understanding potential impacts of complex pollutant profiles to long-lived species such as the green sea turtle (Chelonia mydas), a threatened megaherbivore resident in north Australia. Dietary ingestion may be a key exposure route for metals in these animals and marine plants can accumulate metals at higher concentrations than the surrounding environment. We investigated concentrations of 19 metals and metalloids in C. mydas forage samples collected from a group of offshore coral cays and two coastal bays over a period of 2-3 years. Although no samples exceeded sediment quality guidelines, coastal forage Co, Fe, and V concentrations were up to 2-fold higher, and offshore forage Sr concentrations were ~3-fold higher, than global seagrass means. Principal Component Analysis differentiated coastal bay from coral cay forage according to patterns consistent with underlying terrigenous-type or marine carbonate-type sediment geochemistry, such that coastal bay forage was higher in Fe, Co, Mn, Cu, and Mo (and others) but forage from coral cays was higher in Sr and U. Forage from the two coastal bays was differentiated according to temporal variation in metal profiles, which may be associated with a more episodic sediment disturbance regime in one of the bays. For all study locations, some forage metal concentrations were higher than previously reported in the global literature. Our results suggest that forage metal profiles may be influenced by the presence of some metals in insoluble forms or bound to ultra-fine sediment particles adhered to forage surfaces. Metal concentrations in Great Barrier Reef forage may be present at levels higher than expected from the global seagrass literature and appear strongly influenced by underlying sediment geochemistry.


Asunto(s)
Antozoos , Metales Pesados/análisis , Tortugas , Contaminantes Químicos del Agua/análisis , Animales , Australia , Bahías , Monitoreo del Ambiente , Sedimentos Geológicos
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