Sedimentology and Geochemistry of core sediments from the Ashtamudi estuary and the adjoining coastal plain,central Kerala,India

The evolution of coast through geological time scale is dependent on the transgression-regression event subsequent to the rise or fall of sea level. This event is accounted by investigation of the vertical sediment deposition patterns and their interrelationship for paleo-enviornmental reconstruction. Different methods like sedimentological (grain size and micro-morphological) and geochemical (elemental relationship) analyses as well as radiocarbon dating are generally used to decipher the sea level changes and paleoclimatic conditions of the Quaternary sediment sequence. For the Indian coast with a coastline length of about 7500 km, studies on geological and geomorphological signatures of sea level changes during the Quaternary were reported in general by researchers during the last two decades. However, for the southwest coast of India particularily Kerala which is famous for its coastal landforms comprising of estuaries, lagoons, backwaters, coastal plains, cliffs and barrier beaches, studies pertaining to the marine transgression-regression events in the southern region are limited. The Neendakara-Kayamkulam coastal stretch in central Kerala where the coast is manifested with shore parallel Kayamkulam Lagoon on one side and shore perpendicular Ashtamudi Estuary on the other side indicating existence of an uplifted prograded coastal margin followed by barrier beaches, backwater channels, ridge and runnel topography is an ideal site for studying such events. Hence the present study has been taken up in this context to address the gap area. The location for collection of core samples representing coastal plain, estuarylagoon and offshore regions have been identified based on published literature and available sedimentary records. The objectives of the research work are:  To study the lithological variations and depositional environments of sediment cores along the coastal plain, estuary-lagoon and offshore regions between Kollam and Kayamkulam in the central Kerala coast  To study the transportation and diagenetic history of sediments in the area  To investigate the geochemical characterization of sediments and to elucidate the source-sink relationship  To understand the marine transgression-regression events and to propose a conceptual model for the region The thesis comprises of 8 chapters. The first chapter embodies the preamble for the selection and significance of this research work. The study area is introduced with details on its physiographical, geological, geomorphological, rainfall and climate information. A review of literature, compiling the research on different aspects such as physico-chemical, geomorphological, tectonics, transgression-regression events are presented in the second chapter and they are broadly classified into three viz:- International, National and Kerala. The field data collection and laboratory analyses adopted in the research work are discussed in the third chapter. For collection of sediment core samples from the coastal plains, rotary drilling method was employed whereas for the estuary-lagoon and offshore locations the gravity/piston corer method was adopted. The collected subsurficial samples were analysed for texture, surface micro-texture, elemental analysis, XRD and radiocarbon dating techniques for age determination. The fourth chapter deals with the textural analysis of the core samples collected from various predefined locations of the study area. The result reveals that the Ashtamudi Estuary is composed of silty clay to clayey type of sediments whereas offshore cores are carpeted with silty clay to relict sand. Investigation of the source of sediments deposited in the coastal plain located on either side of the estuary indicates the dominance of terrigenous to marine origin in the southern region whereas it is predominantly of marine origin towards the north. Further the hydrodynamic conditions as well as the depositional enviornment of the sediment cores are elucidated based on statistical parameters that decipher the deposition pattern at various locations viz., coastal plain (open to closed basin), Ashtamudi Estuary (partially open to restricted estuary to closed basin) and offshore (open channel). The intensity of clay minerals is also discussed. From the results of radiocarbon dating the sediment depositional environments were deciphered.The results of the microtextural study of sediment samples (quartz grains) using Scanning Electron Microscope (SEM) are presented in the fifth chapter. These results throw light on the processes of transport and diagenetic history of the detrital sediments. Based on the lithological variations, selected quartz grains of different environments were also analysed. The study indicates that the southern coastal plain sediments were transported and deposited mechanically under fluvial environment followed by diagenesis under prolonged marine incursion. But in the case of the northern coastal plain, the sediments were transported and deposited under littoral environment indicating the dominance of marine incursion through mechanical as well as chemical processes. The quartz grains of the Ashtamudi Estuary indicate fluvial origin. The surface texture features of the offshore sediments suggest that the quartz grains are of littoral origin and represent the relict beach deposits. The geochemical characterisation of sediment cores based on geochemical classification, sediment maturity, palaeo-weathering and provenance in different environments are discussed in the sixth chapter. In the seventh chapter the integration of multiproxies data along with radiocarbon dates are presented and finally evolution and depositional history based on transgression–regression events is deciphered. The eighth chapter summarizes the major findings and conclusions of the study with recommendation for future work.

Thermodynamics and log–contrast analysis in fluid geochemistry

There are two principal chemical concepts that are important for studying the natural environment. The first one is thermodynamics, which describes whether a system is at equilibrium or can spontaneously change by chemical reactions. The second main concept is how fast chemical reactions (kinetics or rate of chemical change) take place whenever they start. In this work we examine a natural system in which both thermodynamics and kinetic factors are important in determining the abundance of NH+4 , NO−2 and NO−3 in superficial waters. Samples were collected in the Arno Basin (Tuscany, Italy), a system in which natural and antrophic effects both contribute to highly modify the chemical composition of water. Thermodynamical modelling based on the reduction-oxidation reactions involving the passage NH+4 -> NO−2 -> NO−3 in equilibrium conditions has allowed to determine the Eh redox potential values able to characterise the state of each sample and, consequently, of the fluid environment from which it was drawn. Just as pH expresses the concentration of H+ in solution, redox potential is used to express the tendency of an environment to receive or supply electrons. In this context, oxic environments, as those of river systems, are said to have a high redox potential because O2 is available as an electron acceptor. Principles of thermodynamics and chemical kinetics allow to obtain a model that often does not completely describe the reality of natural systems. Chemical reactions may indeed fail to achieve equilibrium because the products escape from the site of the rection or because reactions involving the trasformation are very slow, so that non-equilibrium conditions exist for long periods. Moreover, reaction rates can be sensitive to poorly understood catalytic effects or to surface effects, while variables as concentration (a large number of chemical species can coexist and interact concurrently), temperature and pressure can have large gradients in natural systems. By taking into account this, data of 91 water samples have been modelled by using statistical methodologies for compositional data. The application of log–contrast analysis has allowed to obtain statistical parameters to be correlated with the calculated Eh values. In this way, natural conditions in which chemical equilibrium is hypothesised, as well as underlying fast reactions, are compared with those described by a stochastic approach

Searching for the perfect surface area normalizing term - a comparison of BET surface area-, geometric surface area- and mass-normalized dissolution rates of anorthite and biotite

Dissolution rates were calculated for a range of grain sizes of anorthite and biotite dissolved under far from equilibrium conditions at pH 3, T = 20 degrees C. Dissolution rates were normalized to initial and final BET surface area, geometric surface area, mass and (for biotite only) geometric edge surface area. Constant (within error) dissolution rates were only obtained by normalizing to initial BET surface area for biotite. The normalizing term that gave the smallest variation about the mean for anorthite was initial BET surface area. In field studies, only current (final) surface area is measurable. In this study, final geometric surface area gave the smallest variation for anorthite dissolution rates and final geometric edge surface area for biotite dissolution rates. (c) 2005 Published by Elsevier B.V.

Aqueous geochemistry and oxygen isotope compositions of acid mine drainage from the Río Tinto, SW Spain, highlight inconsistencies in current models

The Rio Tinto river in SW Spain is a classic example of acid mine drainage and the focus of an increasing amount of research including environmental geochemistry, extremophile microbiology and Mars-analogue studies. Its 5000-year mining legacy has resulted in a wide range of point inputs including spoil heaps and tunnels draining underground workings. The variety of inputs and importance of the river as a research site make it an ideal location for investigating sulphide oxidation mechanisms at the field scale. Mass balance calculations showed that pyrite oxidation accounts for over 93% of the dissolved sulphate derived from sulphide oxidation in the Rio Tinto point inputs. Oxygen isotopes in water and sulphate were analysed from a variety of drainage sources and displayed delta O-18((SO4-H2O)) values from 3.9 to 13.6 parts per thousand, indicating that different oxidation pathways occurred at different sites within the catchment. The most commonly used approach to interpreting field oxygen isotope data applies water and oxygen fractionation factors derived from laboratory experiments. We demonstrate that this approach cannot explain high delta O-18((SO4-H2O)) values in a manner that is consistent with recent models of pyrite and sulphoxyanion oxidation. In the Rio Tinto, high delta O-18((SO4-H2O)) values (11.2-13.6 parts per thousand) occur in concentrated (Fe = 172-829 mM), low pH (0.88-1.4), ferrous iron (68-91% of total Fe) waters and are most simply explained by a mechanism involving a dissolved sulphite intermediate, sulphite-water oxygen equilibrium exchange and finally sulphite oxidation to sulphate with O-2. In contrast, drainage from large waste blocks of acid volcanic tuff with pyritiferous veins also had low pH (1.7). but had a low delta O-18((SO4-H2O)) value of 4.0 parts per thousand and high concentrations of ferric iron (Fe(III) = 185 mM, total Fe = 186 mM), suggesting a pathway where ferric iron is the primary oxidant, water is the primary source of oxygen in the sulphate and where sulphate is released directly from the pyrite surface. However, problems remain with the sulphite-water oxygen exchange model and recommendations are therefore made for future experiments to refine our understanding of oxygen isotopes in pyrite oxidation. (C) 2009 Elsevier B.V. All rights reserved.

Sea-surface temperature records of Termination 1 in the Gulf of California: Challenges for seasonal and interannual analogues of tropical Pacific climate change

Centennial-scale records of sea-surface temperature and opal composition spanning the Last Glacial Maximum and Termination 1 (circa 25–6 ka) are presented here from Guaymas Basin in the Gulf of California. Through the application of two organic geochemistry proxies, the U37K′ index and the TEX86H index, we present evidence for rapid, stepped changes in temperatures during deglaciation. These occur in both temperature proxies at 13 ka (∼3°C increase in 270 years), 10.0 ka (∼2°C decrease over ∼250 years) and at 8.2 ka (3°C increase in <200 years). An additional rapid warming step is also observed in TEX86H at 11.5 ka. In comparing the two temperature proxies and opal content, we consider the potential for upwelling intensity to be recorded and link this millennial-scale variability to shifting Intertropical Convergence Zone position and variations in the strength of the Subtropical High. The onset of the deglacial warming from 17 to 18 ka is comparable to a “southern hemisphere” signal, although the opal record mimics the ice-rafting events of the north Atlantic (Heinrich events). Neither the modern seasonal cycle nor El Niño/Southern Oscillation patterns provide valid analogues for the trends we observe in comparison with other regional records. Fully coupled climate model simulations confirm this result, and in combination we question whether the seasonal or interannual climate variations of the modern climate are valid analogues for the glacial and deglacial tropical Pacific.

Tropical climates at the Last Glacial Maximum: a new synthesis of terrestrial palaeoclimate data. I. Vegetation, lake-levels and geochemistry.

Palaeodata in synthesis form are needed as benchmarks for the Palaeoclimate Modelling Intercomparison Project (PMIP). Advances since the last synthesis of terrestrial palaeodata from the last glacial maximum (LGM) call for a new evaluation, especially of data from the tropics. Here pollen, plant-macrofossil, lake-level, noble gas (from groundwater) and δ18O (from speleothems) data are compiled for 18±2 ka (14C), 32 °N–33 °S. The reliability of the data was evaluated using explicit criteria and some types of data were re-analysed using consistent methods in order to derive a set of mutually consistent palaeoclimate estimates of mean temperature of the coldest month (MTCO), mean annual temperature (MAT), plant available moisture (PAM) and runoff (P-E). Cold-month temperature (MAT) anomalies from plant data range from −1 to −2 K near sea level in Indonesia and the S Pacific, through −6 to −8 K at many high-elevation sites to −8 to −15 K in S China and the SE USA. MAT anomalies from groundwater or speleothems seem more uniform (−4 to −6 K), but the data are as yet sparse; a clear divergence between MAT and cold-month estimates from the same region is seen only in the SE USA, where cold-air advection is expected to have enhanced cooling in winter. Regression of all cold-month anomalies against site elevation yielded an estimated average cooling of −2.5 to −3 K at modern sea level, increasing to ≈−6 K by 3000 m. However, Neotropical sites showed larger than the average sea-level cooling (−5 to −6 K) and a non-significant elevation effect, whereas W and S Pacific sites showed much less sea-level cooling (−1 K) and a stronger elevation effect. These findings support the inference that tropical sea-surface temperatures (SSTs) were lower than the CLIMAP estimates, but they limit the plausible average tropical sea-surface cooling, and they support the existence of CLIMAP-like geographic patterns in SST anomalies. Trends of PAM and lake levels indicate wet LGM conditions in the W USA, and at the highest elevations, with generally dry conditions elsewhere. These results suggest a colder-than-present ocean surface producing a weaker hydrological cycle, more arid continents, and arguably steeper-than-present terrestrial lapse rates. Such linkages are supported by recent observations on freezing-level height and tropical SSTs; moreover, simulations of “greenhouse” and LGM climates point to several possible feedback processes by which low-level temperature anomalies might be amplified aloft.

Integrated marine gravity field in the Brazilian coast from altimeter-derived sea surface gradient and shipborne gravity

Sea surface gradients derived from the Geosat and ERS-1 satellite altimetry geodetic missions were integrated with marine gravity data from the National Geophysical Data Center and Brazilian national surveys. Using the least squares collocation method, models of free-air gravity anomaly and geoid height were calculated for the coast of Brazil with a resolution of 2` x 2`. The integration of satellite and shipborne data showed better statistical results in regions near the coast than using satellite data only, suggesting an improvement when compared to the state-of-the-art global gravity models. Furthermore, these results were obtained with considerably less input information than was used by those reference models. The least squares collocation presented a very low content of high-frequency noise in the predicted gravity anomalies. This may be considered essential to improve the high resolution representation of the gravity field in regions of ocean-continent transition. (C) 2010 Elsevier Ltd. All rights reserved.

Moho map of South America from receiver functions and surface waves

We estimate crustal structure and thickness of South America north of roughly 40 degrees S. To this end, we analyzed receiver functions from 20 relatively new temporary broadband seismic stations deployed across eastern Brazil. In the analysis we include teleseismic and some regional events, particularly for stations that recorded few suitable earthquakes. We first estimate crustal thickness and average Poisson`s ratio using two different stacking methods. We then combine the new crustal constraints with results from previous receiver function studies. To interpolate the crustal thickness between the station locations, we jointly invert these Moho point constraints, Rayleigh wave group velocities, and regional S and Rayleigh waveforms for a continuous map of Moho depth. The new tomographic Moho map suggests that Moho depth and Moho relief vary slightly with age within the Precambrian crust. Whether or not a positive correlation between crustal thickness and geologic age is derived from the pre-interpolation point constraints depends strongly on the selected subset of receiver functions. This implies that using only pre-interpolation point constraints (receiver functions) inadequately samples the spatial variation in geologic age. The new Moho map also reveals an anomalously deep Moho beneath the oldest core of the Amazonian Craton.

Geochemistry of iron and manganese in soils and sediments of a mangrove system, Island of Pai Matos (Cananeia - SP, Brazil)

Five zones along a transect of 180 m were selected for study on the Island of Pai Matos (Sao Paulo, Brazil). Four of the zones are colonised by vascular plants (Spartina SP, Laguncularia LG, Avicennia AV and Rhizophora RH) and were denominated soils, and the other zone, which lacks vegetation, was denominated sediment (SD). The geochemical conditions differed significantly in soils and sediment and also at different depths. The soils were oxic (Eh > 350 mV) or suboxic (Eh: 350-100 mV) at the surface and anoxic (Eh < 100 mV) at depth, whereas in the sediment anoxic conditions prevailed at all depths, but with a lower concentration of sulphides in the pore water and pyrite in the solid fraction. Under these geochemical conditions Fe is retained in the soils, while the Mn tends to be mobilized and lost. The most abundant form of iron oxyhydroxide was lepidocrocite (mean concentration for all sites and depths, 45 +/- 19 mu mol g(-1)), followed by goethite (30 19 mu mol g(-1))and ferrihydrite (19 +/- 11 mu mol g(-1)),with significant differences among the mean concentrations. There was a significant decrease with depth in all the types of Fe oxyhydroxides measured, particularly the poorly crystalline forms. The pyrite fraction was an important component of the free Fe pool (non-silicate Fe) in all soils as well as in the sediment, especially below 20 cm depth (mean concentration for all sites and depths, 60 +/- 54 mu mol CI). Furthermore, the mean concentration of Fe-pyrite for all sites and depths was higher than that obtained for any of the three Fe oxyhydroxides measured. The Fe-AVS was a minor fraction, indicating that the high concentrations of dissolved Fe in the soils in the upper area of the transect result from the oxidation of Fe sulphides during low tide. Mossbauer spectroscopy also revealed that most of the Fe (III) was associated with silicates, in this case nontronite. The presence of crystals of pyrite associated with phyllosilicates in samples from the upper layer of the soils may indicate that pyritization of this form of Fe(III) is more rapid than usually reported for ocean bed sediments. The sequential extraction of Mn did not reveal any clearly dominant fraction, with the Mn-carbonate fraction being the most prevalent, followed by exchangeable Mn and oxides of Mn, whereas pyrite-Mn and Mn associated with crystalline Fe-oxides were present at significantly lower concentrations. The high concentration of dissolved Mn found in the soils in the lower part of the transect is consistent with the fact that the solubility is determined by the carbonate fraction. Unlike for Fe, in the soils in the higher zone, which are subject to intense drainage during low tide, there was loss of Mn, as reflected by the concentration of total Mn. (C) 2008 Elsevier B.V. All rights reserved.

Multiscale Analysis of Topographic Surface Roughness in the Midland Valley, Scotland

Surface roughness is an important geomorphological variable which has been used in the Earth and planetary sciences to infer material properties, current/past processes, and the time elapsed since formation. No single definition exists; however, within the context of geomorphometry, we use surface roughness as an expression of the variability of a topographic surface at a given scale, where the scale of analysis is determined by the size of the landforms or geomorphic features of interest. Six techniques for the calculation of surface roughness were selected for an assessment of the parameter`s behavior at different spatial scales and data-set resolutions. Area ratio operated independently of scale, providing consistent results across spatial resolutions. Vector dispersion produced results with increasing roughness and homogenization of terrain at coarser resolutions and larger window sizes. Standard deviation of residual topography highlighted local features and did not detect regional relief. Standard deviation of elevation correctly identified breaks of slope and was good at detecting regional relief. Standard deviation of slope (SD(slope)) also correctly identified smooth sloping areas and breaks of slope, providing the best results for geomorphological analysis. Standard deviation of profile curvature identified the breaks of slope, although not as strongly as SD(slope), and it is sensitive to noise and spurious data. In general, SD(slope) offered good performance at a variety of scales, while the simplicity of calculation is perhaps its single greatest benefit.

Geochemical and ecotoxicological assessment for estuarine surface sediments from Southern Brazil

Sediments from Guaratuba Bay (PR, Brazil), a marine protected area, were collected and evaluated for geochemistry and toxicity. High levels of P and acute toxicity were observed in some samples. Concentrations of Cu, Cd, Pb and Zn were relatively low; however, Cd levels eventually exceeded Threshold Effect Level. Toxicities were associated to nutrients and metals enrichment. Results suggest that impacts are incipient and occur only at specific sites, associated to multiple contamination sources. Despite sediments quality seems to range between good and fair, attention is required to land-use planning around Guaratuba Bay and controlling local pollution sources. © 2013 Elsevier Ltd. All rights reserved.

Temporal and Spatial Variations of Ions, Isotopes and Agricultural Contaminants in Surface Waters and Groundwater of Nebraska's Rainwater Basin Wetland Region

The wetlands of south-central Nebraska’s Rainwater Basin region are considered of international importance as a habitat for millions of migratory birds, but are being endangered by agricultural practices. The Rainwater Basin extends across 17 counties and covers 4,000 square miles. The purpose of this study was to assemble baseline chemical data for several representative wetlands across the Rainwater Basin region, and determine the use of these chemical data for investigating groundwater recharge. Eight representative wetlands were chosen across the Rainwater Basin to monitor surface and groundwater chemistry. At each site, a shallow well and deep well were installed and sampled once in the summer of 2009 and again in the spring of 2010. Wetland surface water was sampled monthly from April, 2009 to May, 2010. Waters were analyzed for major ions, nutrients, pesticides and oxygen-18 and deuterium isotopes at the University of Nebraska Water Sciences Laboratory. Geochemical analysis of surface waters presents a range of temporal and spatial variations. Wetlands had variable water volumes, isotopic compositions, ion chemistries and agricultural contaminant levels throughout the year and, except for a few trends, theses variations cannot be predicted with certainty year-to-year or wetland-to-wetland. Isotopic compositions showed evaporation was a contributor to water loss, and thus, did impact water chemistry. Surface water nitrate concentrations ranged from <0.10 to 4.04 mg/L. The nitrate levels are much higher in the groundwater, ranging from <0.10 to 18.4 mg/L, and are of concern because they are found above the maximum contaminant level (MCL) of 10 mg/L. Atrazine concentrations in surface waters ranged from <0.05 to 10.3 ppb. Groundwater atrazine concentrations ranged from <0.05 to 0.28 ppb. The high atrazine concentrations in surface waters are of concern as they are above the MCL of 3 ppb, and the highest levels occur during the spring bird migration. Most sampled groundwaters had detectable tritium indicating a mix of modern (<5 to 10 years old) and submodern (older than 1950s) recharge. The groundwater also had differences in chemical and isotope composition, and in some cases, increased nitrate concentrations, between the two sampling periods. Modern groundwater tritium ages and changes in groundwater chemical and isotopic compositions may indicate connections with surface waters in the Rainwater Basin.

Lipid biomarkers in surface sediments from an unusual coastal upwelling area from the SW Atlantic Ocean

The coastal upwelling off Cabo Frio (SE Brazilian coast, SEBC) represents an exception to the world`s oceans since the majority of the upwelling areas are located in eastern boundary current systems. Cabo Frio represents an interesting area for investigation due to its tight physical-biological interaction and the importance of the region as a major fishery area in the SEBC. We analyzed a suite of lipid biomarkers to apportion the main sources of organic matter in surface sediments of the continental shelf off Cabo Frio, comparing the area to non-upwelling regions off the SEBC (shelf break off Cabo Frio and continental shelf off Ubatuba). During spring and summer (the upwelling period), diatoms are probably the major sources of polyunsaturated fatty acids (PUFAs) and C-28 sterols in surface sediments from Cabo Frio continental shelf. Sediments sampled in winter showed, in contrast, lower relative abundance of PUFAs and higher stanol/stenol ratio values. In deeper regions off Cabo Frio, elevated concentrations of alkenones, 24-methylcholest-5,22E-dien-3 beta-ol and 24-ethylcholest-5-en-3 beta-ol during the spring may be produced by prymnesiophytes or cryptophytes and cyanobacteria, respectively. In Ubatuba, the C-27 and C-28 sterols are likely derived from omnivorous salps and nanoflagellates. At non-upwelling areas, despite the increase in biomarker concentrations during spring and summer, lower concentrations of PUFAs, phytol and algal sterols than in shelf areas off Cabo Frio suggest the importance of the upwelling system to the rapid transfer of organic carbon to surface sediments. Our results suggest that spatial and temporal variability in organic matter production and deposition merits consideration for constraining the carbon budgets in the coastal region off Cabo Frio. (C) 2008 Elsevier Ltd. All rights reserved.

Distribution of major elements in Atlantic surface sediments (36 degrees N-49 degrees S): Imprint of terrigenous input and continental weathering

Numerous studies use major element concentrations measured on continental margin sediments to reconstruct terrestrial climate variations. The choice and interpretation of climate proxies however differ from site to site. Here we map the concentrations of major elements (Ca, Fe, Al, Si, Ti, K) in Atlantic surface sediments (36 degrees N-49 degrees S) to assess the factors influencing the geochemistry of Atlantic hemipelagic sediments and the potential of elemental ratios to reconstruct different terrestrial climate regimes. High concentrations of terrigenous elements and low Ca concentrations along the African and South American margins reflect the dominance of terrigenous input in these regions. Single element concentrations and elemental ratios including Ca (e. g., Fe/Ca) are too sensitive to dilution effects (enhanced biological productivity, carbonate dissolution) to allow reliable reconstructions of terrestrial climate. Other elemental ratios reflect the composition of terrigenous material and mirror the climatic conditions within the continental catchment areas. The Atlantic distribution of Ti/Al supports its use as a proxy for eolian versus fluvial input in regions of dust deposition that are not affected by the input of mafic rock material. The spatial distributions of Al/Si and Fe/K reflect the relative input of intensively weathered material from humid regions versus slightly weathered particles from drier areas. High biogenic opal input however influences the Al/Si ratio. Fe/K is sensitive to the input of mafic material and the topography of Andean river drainage basins. Both ratios are suitable to reconstruct African and South American climatic zones characterized by different intensities of chemical weathering in well-understood environmental settings.