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PubMed2002

Immobilizing humic acid in a sol-gel matrix: a new tool to study humic-contaminants sorption interactions.

Humic substances originated from aquatic, soil, or sediment environments are mixtures of humic compounds with various characteristics. Sorption interactions with isolated, well defined humic fractions can be studied either in an aqueous phase ("dissolved humic substances"), or in a solid-phase, by coating mineral particles with the humic materials, or simply by working with humic acid particles (powder) at low pH to minimize dissolution. Each attitude, by definition, can be studied by different experimental techniques and has a different meaning for understanding natural environmental processes. In this study, a new tool for studying sorption interactions is presented. Sol-gel was used as an inert matrix to immobilize (entrap) various humic acids (HAs), and then used to study the interactions of several polycyclic aromatic hydrocarbons (PAHs) with the entrapped HA. Linear and nonlinear sorption coefficients were highly correlated with contaminant hydrophobicity. Sorption of pyrene to immobilized HA was in the order of soil HA > Aldrich HA approximately = peat HA. It was concluded that the entrapped HAs retained their original properties in the gel matrix and were accessible to the external contaminant through the pore network. Additionally, binding coefficients of pyreneto dissolved humic substances and to dissolved organic matter (DOM) were determined from the reduction in pyrene sorption to immobilized HA in the presence of dissolved humic material or DOM in solution. Binding coefficients of pyrene were in the order of the following: dissolved Aldrich HA > dissolved peat fulvic acid (FA) > DOM derived from mature compost > DOM derived from fresh compost.

Adsorption↗
PubMed2003

Millennial-scale records of atmospheric mercury deposition obtained from ombrotrophic and minerotrophic peatlands in the Swiss Jura Mountains.

Peat cores from two bogs were used to reconstruct changes in net atmospheric mercury deposition in Switzerland for the past 2-3 millennia. The two records were compared to assess the reliability of peat cores as archives of atmospheric mercury deposition. Net mercury accumulation rates and Hg(ex), an indicator of significant anthropogenic mercury contamination, were calculated for both cores. Both records showed stable background values (0.5-1.9 and 1.0-3.0 microg of Hg m(-2) yr(-1)). In both profiles, mercury accumulation rates began to increase during the 12th century, and Hg(ex) appeared during the 14th century. The late 19th and early 20th centuries have been studied in detail. The profiles match well with the history of local and global mercury emissions. The magnitude of increase from the pre-anthropogenic to anthropogenic period was also very similar in both records. Although the two sites are botanically very similar and lie only 3.5 km apart, accumulation rates at TGE were generally higher than those at EGR. This indicates that, although such records can be used to determine the chronologies of and relative changes in rates of atmospheric mercury deposition, differences in rates of mercury accumulation rates between sites do not necessarily indicate differences in deposition rates of mercury from the atmosphere.

Air Pollutants↗
PubMed2003

Influence of humic substances on the removal of pentachlorophenol by a biomimetic catalytic system with a water-soluble iron(III)-porphyrin complex.

To investigate some basic aspects of soil remediation using biomimetic catalysts, the effects of humic substances (HSs) on the removal of xenobiotics, such as pentachlorophenol (PCP), were investigated. The use of a biomimetic catalytic system using tetra(p-sulfophenyl)porphine-iron(III) (Fe(III)-TPPS) and potassium monopersulfate (KHSO5) resulted in the disappearance of PCP, accompanied by dechlorination. In addition, this process was enhanced by the presence of several types of HSs. The degrees of enhancement (% delta(PCP)60) achieved by the presence of HSs from peat and compost soils were larger than those in the presence of other types of HSs (tropical peat, brown forest, and ando soils). In control experiments, no PCP disappearance and dechlorination were observed in the presence of only KHSO5, only Fe(III)-TPPS, or combinations of HSs and either KHSO5 or Fe(III)-TPPS. To better understand the role of added HS in enhancing or inhibiting PCP disappearance, correlations between the chemical parameters of the HSs and % delta(PCP)60 were investigated. The most effective HSs had lower carboxylic acid contents and lower degrees of unsaturation. The carboxylic acid content and degree of unsaturation increase with the extent of humification. Therefore, HSs of a lower degree of humification would be predicted to be more useful in enhancing the disappearance of PCP in an Fe(III)-TPPS/KHSO5 system.

Catalysis↗
PubMed2002

Low nitrogen losses with a new source of nitrogen for cultivation of conifer seedlings.

Losses of nitrogen (N) when cultivating plants may cause a number of adverse environmental effects. N losses from conifer nurseries, for instance, may have a considerable impact on the local environment, and studies indicate that the bulk of added N is not recovered in the cultivated plants. This study was conducted to obtain insight into the causes of the low recovery and to test an alternative N fertilizer. Hence, growth of the economically important Scots pine (Pinus sylvestris (L).) seedlings and the recovery of different forms of added nitrogen (N) were investigated in a greenhouse experiment. Containerized seedlings were grown in peat for one summer, with two different N fertilizers, one organic (arginine) and one inorganic (a commercial fertilizer (CF) containing a mixture of ammonium and nitrate) each at an N concentration of 3 mM. At the end of the growth period, some seedlings were labeled with solutions containing either U-[13C6], [15N4]-arginine, (15NH4)2SO4, or K15NO3 supplied to the growth substrate. Labeled seedlings were harvested 1 h, 5 days, and 19 days after tracer addition, and the recovery of each added nitrogen source in both the seedlings and the growth substrate was measured. The retention of the three N forms during discharge of solutions from the growth substrate, peat, was tested in a separate experiment. Arginine-fed seedlings grew better and had higher needle N concentrations than the CF-fed seedlings. Isotopic data showed that the arginine treatment gave significantly higher N recoveries (80%) compared to the CF treatment (50%). The low recovery of N in the CF treatment was largely due to very low recovery (30%) of NO3- -N. The retention of the different N forms during discharge of solutions from the growth substrate was highest for arginine, somewhat lower for NH44+, and very low for NO3-. The high rate of seedling growth and the small nitrogen losses observed when using arginine suggest that this amino acid may be an efficient and environmentally favorable N source for cultivating conifer seedlings.

Arginine↗
PubMed2003

Biotransformation and accumulation of arsenic in soil amended with seaweed.

For many coastal regions of the world, it has been common practice to apply seaweed to the land as a soil improver and fertilizer. Seaweed is rich in arsenosugars and has a tissue concentration of arsenic up to 100 micro/g g(-1). These arsenic species are relatively nontoxic to humans; however, in the environment they may accumulate in the soil and decompose to more toxic arsenic species. The aim of this study was to determine the fate and biotransformation of these arsenosugars in soil using HPLC-ICP-MS analysis. Data from coastal soils currently manured with seaweeds were used to investigate if arsenic was accumulating in these soils. Long-term application of seaweed increased arsenic concentrations in these soils up to 10-fold (0.35 mg of As kg(-1) for nonagronomic peat, 4.3 mg of As kg(-1) for seaweed-amended peat). The biotransformation of arsenic was studied in microcosm experiments in which a sandy (machair) soil, traditionally manured with seaweed, was amended with Laminaria digitata and Fucus vesiculosus. In both seaweed species, the arsenic occurs in the form of arsenosugars (85%). The application of 50 g of seaweed to 1 kg of soil leads to an increase of arsenic in the soils, and the dominating species found in the soil pore water were dimethylarsinic acid (DMA(V)) and the inorganic species arsenate (As(V)) and arsenite (As(III)) after the initial appearance of arsenosugars. A proposed decomposition pathway of arsenosugars is discussed in which the arsenosugars are transformed to DMA(V) and further to inorganic arsenic without appreciable amounts of methylarsonic acid (MA(V)). Commercially available seaweed-based fertilizers contain arsenic concentration between 10 and 50 mg kg(-1). The arsenic species in these fertilizers depends on the manufacturing procedure. Some contain mainly arsenosugars while others contain mainly DMA(V) and inorganic arsenic. With the application rates suggested by the manufacturers, the application of these fertilizers is 2 orders of magnitude lower than the maximum permissible sewage sludge load for arsenic (varies from 0.025 kg ha(-1) yr(-1) in Styria, Austria, to 0.7 kg ha(-1) yr(-1) in the U.K.), while a direct seaweed application would exceed the maximum arsenic load by at least a factor of 2.

Arsenates↗
PubMed2003

Electrostatic precipitator collection efficiency and trace element emissions from co-combustion of biomass and recovered fuel in fluidized-bed combustion.

Particle and trace element emissions from energy production have continuously been subject to tightening regulations. At the same time, not enough is known on the effect of different combustion processes and different fuels and fuel mixtures on the particle characteristics and particle removal device operation. In this investigation, electrostatic precipitator fractional collection efficiency and trace metal emissions were determined experimentally at a 66 MW biomass-fueled bubbling fluidized-bed combustion plant. The measurements were carried out at the inlet and outlet of the two-field electrostatic precipitator (ESP) at the flue gas temperature of 130-150 degrees C. Two fuel mixtures were investigated: biomass fuel containing 70% wood residue and 30% peat and biomass with recovered fuel containing 70% wood residue, 18% peat, and 12% recovered fuel. The particle mass concentration at the ESP inlet was 510-1400 mg/Nm3. Particle emission at the ESP outlet was 2.3-6.4 mg/Nm3. Total ESP collection efficiency was 99.2-99.8%. Collection efficiency had a minimum in particle size range of 0.1-2 microm. In this size range, collection efficiency was 96-97%. The emission of the trace metals As, Cd, Co, Cr, Cu, Mn, Ni, Pb, Sb, Tl, and V was well below the regulation values set by EU directive for waste incineration and co-incineration.

Air Pollutants↗
PubMed2005

Comparative investigation of low-molecular-weight fulvic acids of different origin by SEC-Q-TOF-ms: new insights into structure and formation.

Size exclusion chromatography (SEC) coupled to electrospray ionization quadrupole time-of-flight mass spectrometry (ESI-Q-TOF-MS) was used to analyze the elemental composition and structure of low-molecular-weight fulvic acid molecules. It is shown that the set of hundreds of individual molecules form a homogeneous and structurally unique class of compounds that can be clearly differentiated from any other class of biogenic matter investigated to date. The molecular composition of low-molecular-weight fulvic acids in isolates of very different origin (surface water, groundwater, peat) is virtually indistinguishable. Significant and characteristic differences are, however, recognized when qualitative information and quantitative information provided by ESI-Q-TOF-MS are linked to each other. The relative frequency of the various molecules in each mixture can differ significantly, with the peat showing higher intensity of the aromatic and less carboxylated molecules of this set, whereas the aquatic fulvic acids show a strong contribution of the molecules with less aromaticity and a higher carboxylate content. The identity of fulvic acid molecules in isolates of different origin implies that no specific source material is required forfulvic acid formation but that they may be formed from different sources by different oxidative processes.

Benzopyrans↗
PubMed2004

Effects of competitor and natural organic matter characteristics on the equilibrium sorption of 1,2-dichlorobenzene in soil and shale.

The competitive sorption behaviors of 1,2-DCB in binary solute systems in four natural sorbents having natural organic matter (NOM) matrixes of different physicochemical characters were investigated in batch reactors. Specifically, the study focused on investigating how the extent of 1,2-DCB competitive sorption depends on (i) the rigidity of NOM matrixes as assessed by the efficiency of chemical oxidation and (ii) the closeness of competitor structure to that of the primary solute. The chemical oxidation and elemental composition results suggest that the shale NOM is the most reduced and condensed, the peat was the most oxidized and amorphous, and two surface soils had intermediate NOM structures. Four chlorinated benzenes and phenanthrene were used as competing solutes. All five chemicals exhibited competition against 1,2-DCB in all sorbents, including the peat, but the extent of competition varied significantly. Little difference in the extent of competition with 1,2-DCB was observed for the various chlorinated benzenes even though some were liquids and some were solids at the experimental temperature. All of the chlorobenzenes were more effective competitors than phenanthrene. The shale showed markedly different competition features from the other sorbents, with a much smaller competitive effect at a given sorbed volume of competitor. However, normalizing sorbed competitor volumes by the capacity of the adsorption domain in the Polanyi-Manes single-solute partition-adsorption model (V0) produced qualitatively similar competitive behavior for each solute; displacement of 1,2-DCB increased with increasing sorbed competitor volumes up to V0, and little additional competition occurred beyond that point. The extent of competition was positively correlated with the maximum adsorption capacity and the fraction of "hard" and "soot" carbon contents as assessed by chemical and thermal oxidation methods. These findings indicate that competition is associated with voids in the NOM structure, that these voids are likely present within the condensed ("hard" plus "soot") carbon domain, and therefore that diagenetic alteration of NOM plays a central role in determining competitive sorption characteristics for hydrophobic contaminants.

Adsorption↗
PubMed2005

Modeling salt-dependent proton binding by organic soils with the NICA-Donnan and Stockholm humic models.

Models are available for simulations of proton dissociation and cation binding by natural organic matter; two examples are the NICA-Donnan and Stockholm Humic (SHM) models. To model proton and metal binding, it is necessary to properly account for the ionic strength dependence of proton dissociation. In previous applications of the models for soils itwas assumed that the electrostatic interactions for solid-phase humic substances were the same as in solution; this assumption was recently challenged. Therefore, we reanalyzed previously published acid-base titrations of acid-washed Sphagnum peat, and we produced additional data sets for two Sphagnum peats and two Spodosol Oe horizons. For the soil suspensions, the original NICA-Donnan and SHM models, which were developed for dissolved humic substances, underestimated the observed salt dependence considerably. When a fixed Donnan volume of 1 L kg(-1) for humic substances in the solid phase was used, the NICA-Donnan model fits were much improved. Also for SHM, slight changes produced improved model fits. The models also produced acceptable simulations of the dissolved Ca, Mg, and Cd concentrations, provided that cation selectivitywas introduced. In conclusion, the proposed extensions to the NICA-Donnan and SHM models were shown to predict the salt dependence of solid-phase humic substances more satisfactorily than earlier model versions.

Humic Substances↗
PubMed2005

Importance of automobile exhaust catalyst emissions for the deposition of platinum, palladium, and rhodium in the northern hemisphere.

An estimated 500 million vehicles worldwide are equipped with an exhaust catalyst that uses platinum group elements (PGE) as the main active components and thus contribute to global PGE emissions. Although PGE emitted from automobile exhaust catalysts were first believed to remain in the roadside environment, we propose here that fine PGE-containing particles in automobile exhaust have resulted in a widespread distribution of emitted PGE. Regional and long-range transport of PGE from automobile exhaust catalysts is supported by elevated PGE deposition in both a peat bog located 250 m from traffic and in central Greenland, respectively. Russian smelters were also found to contribute to PGE contamination in central Greenland. Deposition rates estimated for the roadside environment, the peat bog, and central Greenland were used to provide a first estimate of PGE deposition in the northern hemisphere. The results show that deposition of regionally or long-range transported PGE accounts for a large fraction of total PGE deposition, and PGE deposition in the roadside environment represents less than 5% of the total deposition. Transport at the regional and global scales represents an important component in the environmental cycle of emitted PGE and needs to be further studied to fully assess the environmental fate of PGE from automobile exhaust catalysts.

Aerosols↗
PubMed2006

Binding constants of divalent mercury (Hg2+) in soil humic acids and soil organic matter.

Distribution coefficients (K(OC)) for Hg2+ binding by IHSS Pahokee peat humic acid (PHA) and humic acids separated from O-horizons and peats in a northern temperate forest were determined using a competitive ligand-exchange method. All measurements were made at low ratios of added Hg2+ to reduced S. The commonly used chelating agents, EGTA and DTPA, were found to be ineffective competitive ligands; thus, we used DL-penicillamine, a synthetic amino acid with a thiol group. Calculated free [Hg2+] at equilibrium is very low, ranging from 10(-26.4) at pH 1.9 to 10(-36.9) at pH 5.8. Corresponding log Koc values ranged from 22.6 to 32.8. The slope of the plot of pH versus log K(OC) was 2.68, suggesting that two or more protons are released when each Hg2+ is bound. This is consistent with binding of Hg2+ to bidentate thiol sites with some participation of a third weak-acid group, presumably a thiol. The 1:2 stoichiometry is consistent with X-ray spectroscopy data for Hg2+ bound to HA and with other pH-dependency results showing release of two protons with the binding of each Hg2+. Our K(OC) values are much greater than indicated by the data from most previous studies.

Chelating Agents↗
PubMed2006

Absence of mobile carbohydrate domains in dry humic substances proven by NMR, and implications for organic-contaminant sorption models.

The mobility and domain structure of various standard humic substances have been investigated by 1H and 1H-13C solid-state nuclear magnetic resonance (NMR) experiments. In four dry humic acids, a fulvic acid, a natural organic matter sample, and a whole peat sample, segments that undergo fast, large-amplitude motions account for <9% of the sample. This disproves a previous suggestion, based on 1H NMR data, that flexible domains, presumably carbohydrates, make up >40% of various humic acids; these putative mobile domains were also linked to dual-mode sorption. In particular, neither the polar alkyl (carbohydrate) nor the aromatic components show any fast, large-amplitude mobility. A small fraction of mobile nonpolar alkyl segments identified by us before is the only component undergoing large-amplitude motions, apart from absorbed water that we observe in humic acids exposed to ambient air. 1H-13C wide-line separation NMR shows that, contrary to previous suggestions, the dipolar couplings in the aromatic regions are smaller than in the polar alkyl segments, most likely due to differences in local 1H densities. Series of 1H-13C heteronuclear correlation experiments with 1H spin diffusion reveal close proximity of aromatic and polar alkyl segments in several humic acids, precluding carbohydrate domains on a scale of > 1-nm diameter. In the standard peat humic acid, nonpolar aromatic segments also do not form sorption domains of significant size, while nonpolar aliphatic domains, which we had previously shown to correlate with sorption capacity, have been confirmed.

Adsorption↗
PubMed2006

Suppression of dissolved organic carbon by sulfate induced acidification during simulated droughts.

The relationship between dissolved organic carbon (DOC) and the acidification of soils and freshwaters by sulfate (SO4(2-)) has been a topic of great debate over the last few decades. Most interest has focused on long-term acidification. Few have considered the influence of episodic drought-induced acidification in peatlands on DOC mobility, even through the increased acidity and ionic strength associated with the oxidation of reduced sulfur to SO4(2-) are known to reduce DOC solubility. Reduced DOC concentrations during droughts have often been attributed to: (i) reduced hydrological export; (ii) physicochemical changes in the peat structure; or (iii) changes in the biological production and/or consumption of DOC. Our experimental drought simulations on peat cores showed that SO4(2-) induced acidification reduced DOC concentrations during droughts. However, the relationships between SO4(2-)/pH/ ionic strength and DOC were only apparent when the reductions in observed DOC were expressed as a fraction of the estimated DOC concentration in the absence of SO4(2-), which were derived from soil depth, temperature, and watertable data. This analysis showed that a pH fall from 4.3 to 3.5, due to a SO4(2-) rise from < 2.5 to 35 mg L(-1), caused a 60% reduction in DOC concentrations. In contrast, poor correlations were recorded between S042-/pH/ionic strength and the observed DOC data. As DOC both influences acidity and is influenced by acidity, the relative change in DOC needed to be considered to disentangle the effect of inputs of mineral acids into a system naturally dominated by variable concentrations of organic acids.

Carbon↗
PubMed1999

Biodegradation of gasoline and BTEX in a microaerophilic biobarrier.

Continuous bioremediation of gasoline-contaminated water in a packed-bed biobarrier system under oxygen-limited conditions is discussed. This study was part of an extensive effort to develop an alternative technology for the in situ bioremediation of hydrocarbons where there is a limited supply of oxygen. Protruded stainless steel pieces and granulated peat moss were used as packing material to support microbial growth in two biobarriers. The inoculum was an enrichment culture of an indigenous microbial population from a soil sample. The biobarriers' inlet gasoline concentrations and the linear liquid velocities were similar to those commonly found at in situ conditions. Gasoline removal efficiencies ranged from 94% to 99.9% in the stainless steel-packed biobarrier, and from 86.6% to 99.6% in the peat moss-packed biobarrier. Effluent gasoline concentrations below 0.03 mg/l were obtained at gasoline loading rates less than 27.5 mg/l.d in the stainless steel-packed biobarrier. The remaining fraction of gasoline in the effluent consisted mainly of three aliphatic compounds and not the aromatic compounds. Both biobarrier packings supported near complete removal of the most soluble aromatic hydrocarbons of gasoline (BTEX) under all the conditions examined. The consumption of sulfate and the presence of sulfate-reducing microorganisms suggested the presence of anaerobic metabolism during the degradation of gasoline. Up to 92% gasoline was removed during the first 3 cm of the biobarriers' length.

Anaerobiosis↗
PubMed2002

Analytical electron microscopy as a tool for accessing colloid formation process in natural waters.

Analytical electron microscopy was used to characterize aquatic iron-rich colloids. We focused our attention on a redox transition medium in the drainage water of a peat soil. In the anoxic peat water, observations by transmission electron microscopy and associated energy dispersive analyses (TEM-EDS) highlight the presence of spherical entities (approximately 100-600 nm), containing only traces of iron. The increase of dissolved oxygen concentration favours the formation of iron oxy(hydr)oxides. In the oxygenated drain, particles with the same morphology and size range are present. Statistical TEM-EDS analyses show that they represent the only colloidal form of iron in the drain samples. Nevertheless, although Fe-K peaks appear clearly on EDS spectra, the proportion of iron in these colloids reaches at most 4% at. (whereas C + O > 90% at.). Structural information completes this study. Both electron spectroscopic imaging (ESI) and electron energy-loss spectroscopy (EELS) reveal the disparity between element distributions within the drain entities. Iron and calcium are preferably distributed on the outer sphere of the particle, whereas carbon and oxygen follow the theoretical variation of the signal intensity within a plain sphere. The implication of organic matter as nucleation site for iron precipitation is spectacularly demonstrated by the presence of nanometre-sized iron-rich phases highlighted by EELS line scans.

Colloids↗
PubMed2005

Detection of scavenged material in the guts of predators using monoclonal antibodies: a significant source of error in measurement of predation?

Molecular detection systems used to analyse the gut contents of invertebrate predators have enhanced our understanding of trophic interactions, but do not distinguish between the methods of consumption. Many predators regularly scavenge, which could have profound implications for quantitative analyses of the dynamics of predation. We report the first quantified assessment of the potential error caused by scavenging in post-mortem measurements of predation in a slug-carabid system. An anti-slug monoclonal antibody was able to detect antigens from decayed slugs after surprisingly long periods, significantly longer on relatively sterile peat than on natural soil. On soil the half-life of antibody-detectable slug proteins was 8.2 days while on peat it was 11.5 days. When slugs that had decayed on soil for 100 h were fed to the carabid predator Pterostichus melanarius, slug proteins could still be identified after 6 h (but not 12 h) digestion. Fresh and decayed slug was eaten in equal quantities by the beetles suggesting no aversion to the latter. The results suggest that significant errors may be caused by scavenging leading to inaccurate interpretation of predation rates in the field.

Animals↗
PubMed1999

Feather pecking in groups of growing bantams in relation to floor litter substrate and plumage colour.

1. As part of a programme investigating the causation of pecking damage in fowls, this experiment tested a proposal that birds may receive more feather pecks when their plumage colour contrasts with floor litter colour, because litter particles on plumage (as a consequence of dustbathing) may then have greater stimulus value. 2. Groups consisting of 7 light- and 7 dark-coloured bantams were reared from 1 to 11 weeks of age in pens with either wood shavings (light coloured, n=6) or peat (dark coloured, n=6) floor litter. 3. Feather loss from pecking commenced in the 3rd week of life and increased thereafter, but observed pecking damage scores were not consistent with the hypothesis being tested. 4. Despite many more pecks at birds being seen (over 10 weeks) in the wood shavings groups' (661 at particles on plumage, 1795 not at particles) than in peat groups (205, 787), there was no effect of litter substrate on pecking damage. The only evidence supporting the proposal was the finding that, in groups on wood shavings, significantly more pecks at particles on plumage were directed from light coloured birds towards dark ones, than from light to light, dark to light, or dark to dark. 5. Feather eating was confirmed from the presence of feather material in 2% to 15% of faecal droppings collected from each group at 11 weeks, but these proportions were not correlated with pecking damage scores. 6. The results imply that only some feather pecks/pulls were damaging and only some eaten feathers were pulled from other birds.

Aggression↗
PubMed1994

Parallel application of the experiential analysis technique with subject and hypnotist: a new possibility for measuring interactional synchrony.

The Parallel Experiential Analysis Technique (PEAT), a new method for gathering data on the subjective experiences of both the hypnotist and the subject, is described. The PEAT is an interactional modification of the Experiential Analysis Technique (EAT). Procedural details and methodological observations resulting from the modification of the EAT are discussed. Suggestions on how to characterize the phenomenology of the hypnotic interaction and to determine the degree of interactional synchrony on the subjective level between the hypnotist and subject are made.

Awareness↗