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2.
J Agromedicine ; 28(4): 689-702, 2023 10.
Artigo em Inglês | MEDLINE | ID: mdl-37222378

RESUMO

Farmers experience psychological distress and suicide at consistently higher rates than workers in other industries. A gatekeeper is an individual who has been trained to recognize warning symptoms of possible suicidal ideations in others. Gatekeeper programs are recognized by the federal Substance Abuse and Mental Health Services Administration as a best practice for suicide prevention. While gatekeeper programs offer promise to addressing the increasing worldwide suicide rate, how to develop these networks in communities with largely ingrained stigma and taboo related to mental health and suicide remains unanswered. Three of this study's researchers were part of the development and pilot of an agricultural community gatekeeper program and questioned how gatekeeper instructor psychological comfort could be conceptualized and operationalized for the purpose of informing gatekeeper instructor recruitment and training. After a thorough review of the literature, the researchers constructed a conceptual developmental model of gatekeeper instructor comfort and created a Gatekeeper Instructor Comfort Measure instrument which was then piloted with Kentucky K-12 and university agricultural educators. The researchers of this study employed the Rasch model to determine whether the developmental model of gatekeeper instructor comfort held together empirically. Infit and outfit mean squares (0.73 to 1.33) indicate that the items measure one construct, or are unidimensional, while person reliability and separation statistics indicate that the Gatekeeper Instructor Comfort Measure is composed of enough items to differentiate respondents into almost four strata of gatekeeper comfort. The Gatekeeper Instructor Comfort Measure's fit to the Rasch model indicates that the instrument meets the requirements of invariant measurement and should serve as a useful measure for other researchers. The instrument's item difficulty hierarchy also serves as a guide for those training gatekeepers on how to target different gatekeeper outcomes sequentially or developmentally. Researchers recommend restructuring item responses to enable greater discrimination between categories and then piloting the instrument again with a more diverse sample. The revised measure could be used pre- and post-gatekeeper instructor training to determine the impact of training on gatekeeper comfort.


Assuntos
Prevenção do Suicídio , Suicídio , Humanos , Reprodutibilidade dos Testes , Suicídio/psicologia , Ideação Suicida , Saúde Mental
3.
Nat Ecol Evol ; 7(4): 610-622, 2023 04.
Artigo em Inglês | MEDLINE | ID: mdl-37012380

RESUMO

In the past, when scientists encountered and studied 'new' environmental phenomena, they rarely considered the existing knowledge of First Peoples (also known as Indigenous or Aboriginal people). The scientific debate over the regularly spaced bare patches (so-called fairy circles) in arid grasslands of Australian deserts is a case in point. Previous researchers used remote sensing, numerical modelling, aerial images and field observations to propose that fairy circles arise from plant self-organization. Here we present Australian Aboriginal art and narratives, and soil excavation data, that suggest these regularly spaced, bare and hard circles in grasslands are pavement nests occupied by Drepanotermes harvester termites. These circles, called linyji (Manyjilyjarra language) or mingkirri (Warlpiri language), have been used by Aboriginal people in their food economies and for other domestic and sacred purposes across generations. Knowledge of the linyji has been encoded in demonstration and oral transmission, ritual art and ceremony and other media. While the exact origins of the bare circles are unclear, being buried in deep time and Jukurrpa, termites need to be incorporated as key players in a larger system of interactions between soil, water and grass. Ecologically transformative feedbacks across millennia of land use and manipulation by Aboriginal people must be accounted for. We argue that the co-production of knowledge can both improve the care and management of those systems and support intergenerational learning within and across diverse cultures.


Assuntos
Isópteros , Humanos , Animais , Austrália , Solo , Plantas , Poaceae
4.
Sci Total Environ ; 795: 148854, 2021 Nov 15.
Artigo em Inglês | MEDLINE | ID: mdl-34328920

RESUMO

For the past two centuries coastal zones have been suffering seagrass loss resulting in a network of vegetated patches which are barely interconnected and which may compromise the ecological services provided by the canopy. To optimize management efforts for successful restoration strategies, questions need to be addressed about what appropriate canopy architectural considerations are required under certain hydrodynamic conditions. In this study, a set of laboratory experiments were conducted in which hydrodynamic conditions, plant densities and vegetated patch lengths were varied to determine minimum patch lengths for successful management strategies. Based on the TKE production, this study finds two possible canopy behaviours of seagrasses under oscillating flows: one where plants do not interact with the flow and the other where they interact with waves and produce TKE. A threshold from the first to second behaviour occurs for [Formula: see text] = 2, where CD is the drag of the vegetated patch, n is the number of stems per m2, d is the stem diameter and ϕ is the solid plant fraction. Therefore, high canopy densities, large patches of vegetation or moderate wave velocities will produce plant-wave interaction, whereas low canopy densities, small vegetation patches or slow wave velocities will produce a behaviour akin to the non-vegetated cases.


Assuntos
Ecossistema , Hidrodinâmica
5.
Sci Total Environ ; 723: 138020, 2020 Jun 25.
Artigo em Inglês | MEDLINE | ID: mdl-32217386

RESUMO

Estimating gross primary production and ecosystem respiration from oxygen data is performed widely in aquatic systems, yet these estimates can be challenged by high advective fluxes of oxygen. In this study, we develop a hybrid framework linking data-driven and process-based modelling to examine the effect of storm events on oxygen budgets in a constructed wetland. After calibration against measured flow and water temperature data over a two-month period with three storm events, the model was successfully validated against high frequency dissolved oxygen (DO) data exhibiting large diurnal fluctuations. The results demonstrated that pulses of high-DO water injected into the wetland during storm events were able to dramatically change the wetland oxygen budget. A shift was observed in the dominant oxygen inputs, from benthic net production during non-storm periods, to inflows of oxygen during storm events, which served to dampen the classical diurnal oxygen signature. The model also demonstrated the changing balance of pelagic versus benthic production and hypoxia extent in response to storm events, which has implications for the nutrient attenuation performance of constructed wetlands. The study highlights the benefit of linking analysis of high-frequency oxygen data with process-based modelling tools to unravel the varied responses of components of the oxygen budget to storm events.

6.
Water Res ; 153: 11-20, 2019 04 15.
Artigo em Inglês | MEDLINE | ID: mdl-30685632

RESUMO

When acidic groundwater flows into an aquatic system the sediment water interface (SWI) acts as a transition zone between the groundwater and lake water, and often exhibits strong physical and biogeochemical gradients. The fate of groundwater-borne solutes, such as Fe(II), is determined by the balance between the exposure time during transport across the SWI and the reaction time within the SWI, however the relative role of groundwater seepage rates and iron kinetics on acidity generation in lakes is unknown. Porewater seepage velocities, porewater chemical profiles, and limnological data were collected across multiple field campaigns over the last two decades, in acid Mine Lake 77, in Lusatia, Germany. This rare data set was analyzed using a Damköhler approach that compares exposure and reactions timescales, to determine that Fe(II) would typically be transported with little reaction across the SWI, spatially separating it from sediment-processes that produce alkalinity and providing a source of acidity to the lake. This Damköhler analysis further showed that remediation should be focused on reducing groundwater seepage velocities and enhancing exposure times. Strategic planting of submerged benthic macroalgae would slow groundwater inflows, as well as oxygenating overlying waters and supplying organic matter to the sediments. A similar Damköhler analysis could be used to assess the fate of any groundwater-borne reactive chemicals (e.g. phosphorus) into lakes and streams.


Assuntos
Água Subterrânea , Poluentes Químicos da Água , Compostos Ferrosos , Sedimentos Geológicos , Alemanha , Ferro , Cinética , Lagos
7.
PLoS One ; 13(8): e0201737, 2018.
Artigo em Inglês | MEDLINE | ID: mdl-30133481

RESUMO

Canopy fragmentation increases both spatial heterogeneity and patch edges which, in turn, is then likely to modify the local hydrodynamics in the canopy. The orientation of the edge versus the wave and current field is also expected to play an important role in determining wave attenuation and sheltering at the edge of a canopy. We investigated the effect a longitudinal edge (i.e. with its main axis aligned to wave direction) of a simulated canopy has on local edge hydrodynamics. The effect that both canopy density and flexibility have on the hydrodynamics was studied. Flexible plants reduced the wave velocity and the turbulent kinetic energy with distance into the canopy and this attenuation increased as the density of the canopy increased. Compared to flexible plants, an edge of rigid plants produced a higher wave velocity attenuation coupled with an increase in the turbulent kinetic energy with distance into the canopy despite having the same canopy density. This greater wave attenuation at the edge coincided with the shifting of the associated mean current that, in turn, produced an increase in the turbulent kinetic energy at the edge in the canopy. The effect was accentuated when the canopy density increased. The wave velocity attenuation was a linear function of the canopy cover. While flexible plants reduced the turbulent kinetic energy following a linear function of the canopy cover, rigid canopies increased the turbulent kinetic energy following a linear function of the canopy cover. In the case of the flexible vegetation, the lengths of both the inner and outer canopy boundary layers increased as the canopy cover increased.


Assuntos
Hidrodinâmica , Oceanos e Mares , Ecossistema , Desenvolvimento Vegetal
8.
Front Plant Sci ; 8: 2097, 2017.
Artigo em Inglês | MEDLINE | ID: mdl-29276526

RESUMO

Submerged macrophytes can have a profound effect on shallow lake ecosystems through their ability to modify the thermal structure and dissolved oxygen levels within the lake. Invasive macrophytes, in particular, can grow rapidly and induce thermal gradients in lakes that may substantially change the ecosystem structure and challenge the survival of aquatic organisms. We performed fine-scale measurements and 3D numerical modeling at high spatiotemporal resolution to assess the effect of the seasonal growth of Potamogeton crispus L. on the spatial and temporal dynamics of temperature and dissolved oxygen in a shallow urban lake (Lake Monger, Perth, WA, Australia). Daytime stratification developed during the growing season and was clearly observed throughout the macrophyte bed. At all times measured, stratification was stronger at the center of the macrophyte bed compared to the bed edges. By fitting a logistic growth curve to changes in plant height over time (r2 = 0.98), and comparing this curve to temperature data at the center of the macrophyte bed, we found that stratification began once the macrophytes occupied at least 50% of the water depth. This conclusion was strongly supported by a 3D hydrodynamic model fitted to weekly temperature profiles measured at four time periods throughout the growing season (r2 > 0.78 at all times). As the macrophyte height increased and stratification developed, dissolved oxygen concentration profiles changed from vertically homogeneous oxic conditions during both the day and night to expression of night-time anoxic conditions close to the sediments. Spatially interpolated maps of dissolved oxygen and 3D numerical modeling results indicated that the plants also reduced horizontal exchange with surrounding unvegetated areas, preventing flushing of low dissolved oxygen water out of the center of the bed. Simultaneously, aerial imagery showed central dieback occurring toward the end of the growing season. Thus, we hypothesized that stratification-induced anoxia can lead to accelerated P. crispus dieback in this region, causing formation of a ring-shaped pattern in spatial macrophyte distribution. Overall, our study demonstrates that submerged macrophytes can alter the thermal characteristics and oxygen levels within shallow lakes and thus create challenging conditions for maximizing their spatial coverage.

9.
Environ Sci Technol ; 51(17): 9864-9875, 2017 Sep 05.
Artigo em Inglês | MEDLINE | ID: mdl-28813138

RESUMO

Assessment of water quality evolution in the thousands of existing and future mine pit lakes worldwide requires new numerical tools that integrate geochemical, hydrological, and biological processes. A coupled model was used to test alternative hypothesized controls on water quality in a pit lake over ∼8 years. The evolution of pH, Al, and Fe were closely linked; field observations were reproduced with generic solubility equilibrium controls on Fe(III) and Al and a commonly reported acceleration of the abiotic Fe(II) oxidation rate by 2-3 orders of magnitude. Simulations indicated an ongoing acidity loading at the site, and the depletion of Al mineral buffering capacity after ∼5 years. Simulations also supported the existence of pH limitation on nitrification, and a limitation on phytoplankton growth other than the commonly postulated P and DIC limitations. Furthermore, the model reproduced the general patterns of salinity, pH, Al, and Fe during an uncontrolled river breach in 2011, however, incorporating sediment biogeochemical feedbacks is required to reproduce the observed postbreach internal alkalinity generation in the lake. The modeling approach is applicable to the study of hydrological, geochemical, and biological interactions for a range of lake and reservoir management challenges.


Assuntos
Compostos Férricos , Lagos , Qualidade da Água , Ecologia , Hidrobiologia , Hidrodinâmica
10.
Sci Total Environ ; 598: 1001-1014, 2017 Nov 15.
Artigo em Inglês | MEDLINE | ID: mdl-28468117

RESUMO

Among different Water Sensitive Urban Design options, constructed wetlands (CWs) are used to protect and restore downstream water quality by attenuating nutrients generated by stormwater runoff. This research compared the nutrient attenuation ability during a diverse population of storm events of two CWs: (a) a hybrid CW with multiple alternating surface flow (SF) and laterite-based subsurface flow (SSF) compartments, and (b) a single stage SF CW. Within-storm variability, nutrient concentrations were assessed at 2 to 3-h intervals at both the main inlet and outlet of each CW. Dissolved oxygen concentrations of the surface waters were also monitored at 10-min intervals using high frequency in situ sensors. Nutrient loads into the CWs were observed to be higher when a high rainfall event occurred, particularly after longer antecedent dry conditions. Longer hydraulic retention times promoted higher attenuation at both sites. However, the relative extent of nutrient attenuation differed between the CW types; the mean total nitrogen (TN) attenuation in the hybrid and SF CW was 45 and 48%, respectively. The hybrid CW attenuated 67% total phosphorus (TP) loads on average, while the SF CW acted as a net TP source. Periodic storm events transitioned the lentic CW into a lotic CW and caused riparian zone saturation; it was therefore hypothesized that such saturation of organic matter rich-riparian zones led to release of TP in the system. The hybrid CW attenuated the released TP in the downstream laterite-based SSF compartments. Diel oxygen metabolism calculated before and after the storm events was found to be strongly correlated with water temperature, solar exposure and antecedent dry condition during the pre-storm conditions. Furthermore, the SF CW showed a significant relationship between overall nutrient load attenuation and the change in oxygen metabolism during the storm perturbation, suggesting oxygen variation could be a useful proxy indicator of CW function.

11.
Water Res ; 107: 66-82, 2016 Dec 15.
Artigo em Inglês | MEDLINE | ID: mdl-27837734

RESUMO

Among different Water Sensitive Urban Design (WSUD) options, constructed wetlands (CWs) are widely used to protect and support downstream urban waterways from stormwater nutrients. This analysis assessed the nutrient attenuation ability of a novel CW in Western Australia that combined multiple alternating surface flow (SF) and laterite-based subsurface flow (SSF) compartments within a parkland context to improve the urban landscape and amenity. The CW was designed to maximise nutrient reduction despite experiencing a large range of hydrologic conditions, from low transit time nutrient-rich pulses during the wet periods to prolonged low to zero flow conditions during the dry periods. The CW design was further complicated by the possibility of ungauged water inputs after wet antecedent conditions, seasonal macrophyte senescence and a recirculation system to maintain flow during the dry periods. From analysis of data over a range of time scales, we determined that overall the CW attenuated up to 62% total nitrogen (TN) and 99% total phosphorus (TP) loads during dry weather conditions, and 54-76% TN and 27-68% TP during episodic flow pulses. N species attenuation was dominant in the SF compartments, while P species were attenuated mostly within the SSF compartments. Nutrient accumulation in the sediments, and above and below ground biomass of the macrophytes were found to increase during the early stages of operation, suggesting the system reached equilibrium within four years. Further, by comparing trends in nutrient attenuation within the context of diel changes in high frequency oxygen data from different compartments, it was demonstrated that changes in dissolved oxygen were related to changes in nutrient concentration across the CW, although interpretation of this was complicated by changing hydro-climatological conditions. The implementation of this CW concept in a highly seasonal Mediterranean climate demonstrates that urban liveability and environmental health can both be improved through careful design.


Assuntos
Fósforo , Áreas Alagadas , Nitrogênio , Eliminação de Resíduos Líquidos , Movimentos da Água , Purificação da Água
12.
PLoS One ; 11(5): e0156264, 2016.
Artigo em Inglês | MEDLINE | ID: mdl-27227321

RESUMO

The systematic creation of gaps within canopies results in fragmentation and the architecture of fragmented canopies differs substantially from non-fragmented canopies. Canopy fragmentation leads to spatial heterogeneity in hydrodynamics and therefore heterogeneity in the sheltering of canopy communities. Identifying the level of instability due to canopy fragmentation is important for canopies in coastal areas impacted by human activities and indeed, climate change. The gap orientation relative to the wave direction is expected to play an important role in determining wave attenuation and sheltering. Initially we investigated the effect of a single transversal gap within a canopy (i.e. a gap oriented perpendicular to the wave direction) on hydrodynamics, which was compared to fully vegetated canopies (i.e. no gaps) and also to bare sediment. The wave velocity increased with gap width for the two canopy densities studied (2.5% and 10% solid plant fraction) reaching wave velocities found over bare sediments. The turbulent kinetic energy (TKE) within the gap also increased, but was more attenuated by the adjacent vegetation than the wave velocity. As expected, denser canopies produced a greater attenuation of both the wave velocity and the turbulent kinetic energy within an adjacent gap, compared to sparse canopies. Using non-dimensional analysis and our experimental data, a parameterization for predicting TKE in a canopy gap was formulated, as a function of easily measured variables. Based on the experimental results, a fragmented canopy model was then developed to determine the overall mixing level in such canopies. The model revealed that canopies with large gaps present more mixing than canopies with small gaps despite having the same total gap area in the canopy. Furthermore, for the same total gap area, dense fragmented canopies provide more shelter than sparse fragmented canopies.


Assuntos
Ecossistema , Hydrocharitaceae/fisiologia , Hidrodinâmica , Modelos Teóricos , Biomassa , Sedimentos Geológicos , Movimentos da Água
13.
Environ Microbiol Rep ; 8(1): 58-67, 2016 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-26524974

RESUMO

We investigated the microbial community compositions in two sediment samples from the acidic (pH ∼3) and hypersaline (>4.5% NaCl) surface waters, which are widespread in Western Australia. In West Dalyup River, large amounts of NaCl, Fe(II) and sulfate are brought by the groundwater into the surface run-off. The presence of K-jarosite and schwertmannite minerals in the river sediments suggested the occurrence of microbial Fe(II) oxidation because chemical oxidation is greatly reduced at low pH. 16S rRNA gene diversity analyses revealed that sequences affiliated with an uncultured archaeal lineage named Aplasma, which has the genomic potential for Fe(II) oxidation, were dominant in both sediment samples. The acidophilic heterotrophs Acidiphilium and Acidocella were identified as the dominant bacterial groups. Acidiphilium strain AusYE3-1 obtained from the river sediment tolerated up to 6% NaCl at pH 3 under oxic conditions and cells of strain AusYE3-1 reduced the effects of high salt content by forming filamentous structure clumping as aggregates. Neither growth nor Fe(III) reduction by strain AusYE3-1 was observed in anoxic salt-containing medium. The detection of Aplasma group as potential Fe(II) oxidizers and the inhibited Fe(III)-reducing capacity of Acidiphilium contributes to our understanding of the microbial ecology of acidic hypersaline environments.


Assuntos
Ácidos/análise , Archaea/classificação , Bactérias/classificação , Sedimentos Geológicos/química , Sedimentos Geológicos/microbiologia , Microbiota/efeitos dos fármacos , Cloreto de Sódio/análise , Archaea/efeitos dos fármacos , Archaea/metabolismo , Bactérias/efeitos dos fármacos , Bactérias/metabolismo , Análise por Conglomerados , DNA Arqueal/química , DNA Arqueal/genética , DNA Bacteriano/química , DNA Bacteriano/genética , DNA Ribossômico/química , DNA Ribossômico/genética , Ferro/metabolismo , Oxirredução , Filogenia , RNA Ribossômico 16S/genética , Rios , Análise de Sequência de DNA , Austrália Ocidental
14.
Water Res ; 55: 83-94, 2014 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-24602863

RESUMO

Extremely acidic and saline groundwater occurs naturally in south-western Australia. Discharge of this water to surface waters has increased following extensive clearing of native vegetation for agriculture and is likely to have negative environmental impacts. The use of passive treatment systems to manage the acidic discharge and its impacts is complicated by the region's semi-arid climate with hot dry summers and resulting periods of no flow. This study evaluates the performance of a pilot-scale compost bioreactor treating extremely acidic and saline drainage under semi-arid climatic conditions over a period of 2.5 years. The bioreactor's substrate consisted of municipal waste organics (MWO) mixed with 10 wt% recycled limestone. After the start-up phase the compost bioreactor raised the pH from ≤3.7 to ≥7 and produced net alkaline outflow for 126 days. The bioreactor removed up to 28 g/m(2)/d CaCO3 equivalent of acidity and acidity removal was found to be load dependent during the first and third year. Extended drying over summer combined with high salinity caused the formation of a salt-clay surface layer on top of the substrate, which was both beneficial and detrimental for bioreactor performance. The surface layer prevented the dehydration of the substrate and ensured it remained waterlogged when the water level in the bioreactor fell below the substrate surface in summer. However, when flow resumed the salt-clay layer acted as a barrier between the water and substrate decreasing performance efficiency. Performance increased again when the surface layer was broken up indicating that the negative climatic impacts can be managed. Based on substrate analysis after 1.5 years of operation, limestone dissolution was found to be the dominant acidity removal process contributing up to 78-91% of alkalinity generation, while bacterial sulfate reduction produced at least 9-22% of the total alkalinity. The substrate might last up to five years before the limestone is exhausted and would need to be replenished. The MWO substrate was found to release metals (Zn, Cu, Pb, Ni and Cr) and cannot be recommended for use in passive treatment systems unless the risk of metal release is addressed.


Assuntos
Reatores Biológicos , Poluentes Químicos da Água/metabolismo , Ácidos , Clima Desértico , Monitoramento Ambiental , Água Subterrânea/análise
15.
Environ Sci Technol ; 44(17): 6698-705, 2010 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-20695491

RESUMO

Water-sediment interactions triggered by the injection of oxidized aqueous solutions into anoxic groundwater systems usually modify both the aquifer matrix and control the final aqueous composition. The identification and quantification of these reactions in complex heterogeneous systems remains a challenge for the analysis and prediction of water quality changes. Driven by the proposed injection of large quantities of oxic water into a deep anoxic heterogeneous pyritic aquifer; this study was undertaken to quantify the reactivity of aquifer sediments with respect to oxidant consumption and to characterize the variability of the reaction rates across different lithological units. A total of 53 samples were incubated for periods of 14, 37, and 50 days, during which the gas-phase was continuously monitored and the aqueous composition analyzed. A geochemical modeling framework was developed that incorporated a mixed set of equilibrium and kinetic reactions and supported the interpretation and quantification of the geochemical controls. The good agreement between simulated and experimental results of O2 consumption, CO2 production, pH, major ions, and trace metals suggests that the framework was able to successfully quantify reaction rates of competing redox and buffering reactions for the different lithological aquifer material.


Assuntos
Sedimentos Geológicos/química , Modelos Químicos , Substâncias Redutoras/química , Água/química , Calibragem , Dióxido de Carbono/análise , Precipitação Química , Simulação por Computador , Gases/química , Cinética , Consumo de Oxigênio , Transição de Fase , Oligoelementos/análise
16.
Environ Sci Technol ; 43(17): 6548-52, 2009 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-19764215

RESUMO

In large areas of Western Australia, acidic groundwaters occur with pH values distinctly lower than 3, generation of which has been attributed to the oxidation of Fe(II). Incubation experiments performed with sediments from playas receiving acid groundwater demonstrated occurrence of reductive dissolution of ferric iron minerals at rates [670 nmol (g reactive iron)(-1) h(-1)] similar to those observed in sediments of acidic mining lakes (AML), indicating thatthe pH was established through an acidity-driven iron cycle in analogy to processes occurring in AML systems. The low pH values observed in acidic groundwaters and AML, however, can only be achieved if the anion corresponding to Fe(III) is that of a strong acid. In AML, sulfate is derived from pyrite oxidation. Because this process is reported not to occur in the acidic groundwater systems of Western Australia, we have derived a conceptual model according to which sulfate is generated upon reaction of weathering-derived alkalinity with gypsum to form calcite, which is abundant in these areas. The model proposes that part of the alkalinity generated during weathering is stared as calcite in the landscape, which leads to spatial separation of acidity and alkalinity.


Assuntos
Ácidos/química , Compostos Férricos/análise , Água Doce/análise , Modelos Químicos , Poluentes Químicos da Água/análise , Álcalis/química , Carbonato de Cálcio/química , Sulfato de Cálcio/química , Monitoramento Ambiental , Compostos Férricos/química , Água Doce/química , Concentração de Íons de Hidrogênio , Oxirredução , Poluentes Químicos da Água/química , Austrália Ocidental
17.
Dalton Trans ; (13): 1710-20, 2008 Apr 07.
Artigo em Inglês | MEDLINE | ID: mdl-18354768

RESUMO

Single-crystal structural characterizations confirm the existence of the unusual 1 : 4 copper(I) halide : unidentate ligand adducts [Cu(CNt-Bu)4]X for X = Cl, Br (two forms), I (the chloride and one form of the bromide being solvated) with crystal packing dominated by stacks of interleaving cations. Cu-C range between 1.941(2) and 1.972(4) A. The structure of the 1 : 2 chloride complex is also recorded, being [ClCu(CNt-Bu)2], with the copper(I) atom environment trigonal planar, while CuCN : (CNt-Bu) (1 : 1) is a single-stranded polymer which spirals about a crystallographic 3-axis (CN scrambled), the ligands being pendant from the ...CuCNCuCN... string. The (5Cu static broadline NMR spectra of [Cu(CNt-Bu)4]I and [Cu(CNt-Bu)4]Br.H2O in the solid state exhibit dominant, narrow -1/2 <--> +1/2 central transition resonances and associated +/-1/2 <--> +/-3/2 satellite transition resonances which are characteristic of first-order quadrupole broadened systems, while associated high-resolution 65Cu MAS NMR data provide accurate measurement of the 65Cu isotropic chemical shifts. Both approaches provide complete data on the quadrupole and chemical shift interactions which contribute to these spectra. Far-IR spectra of products of reactions involving a range of CuX : t-BuNC ratios reveal the existence of 1 : 1.5 adducts for X = Br, I. Metal-carbon and metal-halogen bands are assigned in the far-IR spectra, which indicate a binuclear double halogen-bridged structure for the 1 : 1.5 complexes.


Assuntos
Cobre/química , Halogênios/química , Nitrilas/química , Compostos Organometálicos/química , Varredura Diferencial de Calorimetria , Cobre/metabolismo , Halogênios/metabolismo , Espectroscopia de Ressonância Magnética , Nitrilas/metabolismo , Compostos Organometálicos/síntese química , Espectrofotometria Infravermelho , Análise Espectral Raman , Termogravimetria
18.
J Environ Qual ; 31(3): 822-8, 2002.
Artigo em Inglês | MEDLINE | ID: mdl-12026085

RESUMO

Oxic resuspension occurs regularly in shallow lakes, yet its role as a mechanism for contaminant remobilization remains ill defined. This study investigated contaminant remobilization during sediment resuspension and determined whether changes in contaminant sediment partitioning reflected the mechanisms controlling remobilization. Arsenic-contaminated sediment from a shallow wetland was subjected to simulated resuspension under a range of differing initial pH conditions. The effect of resuspension on As partitioning was evaluated using a fractionation scheme targeting the dissolved, ion exchangeable, carbonate, organic, amorphous iron oxide, crystalline iron oxide, and apatite fractions. Rate investigations demonstrated that arsenic remobilization occurred on timescales similar to resuspension events, with concentrations reaching steady state within 24 h. The sediment also buffered slurry pH to 8.3 in experiments where the initial pH was between 4 and 10. This pH regulation was attributed to carbonate dissolution or acid-base equilibria of surface base functional groups, although iron oxide and organic matter dissolution did occur in experiments with an initial pH outside this range. Remobilization caused losses in arsenic associated with the ion exchangeable, organic, and amorphous iron fractions but changes in initial pH have a negligible effect on arsenic remobilization or partitioning within the well-buffered region. Resuspension released approximately 20% of the total sediment arsenic, although calculations indicated that a single resuspension event would not significantly change water column arsenic concentrations. While not conclusively proving the mechanisms of remobilization, fractionation gave valuable insight into the effect of sediment resuspension on contaminant remobilization.


Assuntos
Arsênio/química , Poluentes Químicos da Água/análise , Fracionamento Químico , Água Doce , Sedimentos Geológicos , Humanos , Concentração de Íons de Hidrogênio , Equilíbrio Postural , Suspensões , Poluição da Água/prevenção & controle
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