Manganese Oxidation States in Volcanic Soils across Annual Rainfall Gradients.

Manganese (Mn) exists as Mn(II), Mn(III), or Mn(IV) in soils, and the Mn oxidation state controls the roles of Mn in numerous environmental processes. However, the variations of Mn oxidation states with climate remain unknown. We determined the Mn oxidation states in highly weathered bulk volcanic soils (primary minerals free) across two rainfall gradients covering mean annual precipitation (MAP) of 0.25-5 m in the Hawaiian Islands. With increasing MAP, the soil redox conditions generally shifted from oxic to suboxic and to anoxic despite fluctuating at each site; concurrently, the proportions of Mn(IV) and Mn(II) decreased and increased, respectively. Mn(III) was low at both low and high MAP, but accumulated substantially, up to 80% of total Mn, in soils with prevalent suboxic conditions at intermediate MAP. Mn(III) was likely hosted in Mn(III,IV) and iron(III) oxides or complexed with organic matter, and its distribution among these hosts varied with soil redox potentials and soil pH. Soil redox conditions and rainfall-driven leaching jointly controlled exchangeable Mn(II) in soils, with its concentration peaking at intermediate MAP. The Mn redox chemistry was at disequilibrium, with the oxidation states correlating with long-term average soil redox potentials better than with soil pH. The soil redox conditions likely fluctuated between oxic and anoxic conditions more frequently at intermediate than at low and high MAP, creating biogeochemical hot spots where Mn, Fe, and other redox-sensitive elements may be actively cycled.

Relating mineral-organic matter stabilization mechanisms to carbon quality and age distributions using ramped thermal analysis.

Organic carbon (OC) association with soil minerals stabilizes OC on timescales reflecting the strength of mineral-C interactions. We applied ramped thermal oxidation to subsoil B horizons with different mineral-C associations to separate OC according to increasing temperature of oxidation, i.e. thermal activation energy. Generally, OC released at lower temperatures was richer in bioavailable forms like polysaccharides, while OC released at higher temperatures was more aromatic. Organic carbon associated with pedogenic oxides was released at lower temperatures and had a narrow range of 14C content. By contrast, N-rich compounds were released at higher temperatures from samples with 2 : 1 clays and short-range ordered (SRO) amorphous minerals. Temperatures of release overlapped for SRO minerals and crystalline oxides, although the mean age of OC released was older for the SRO. In soils with more mixed mineralogy, the added presence of older OC released at temperatures greater than 450°C from clays resulted in a broader distribution of OC ages within the sample, especially for soils rich in 2 : 1 layer expandable clays such as smectite. While pedogenic setting affects mineral stability and absolute OC age, mineralogy controls the structure of OC age distribution within a sample, which may provide insight into model structures and OC dynamics under changing conditions. This article is part of the Theo Murphy meeting issue 'Radiocarbon in the Anthropocene'.

Alzheimer's disease amyloid-ß pathology in the lens of the eye.

Neuropathological hallmarks of Alzheimer's disease (AD) include pathogenic accumulation of amyloid-ß (Aß) peptides and age-dependent formation of amyloid plaques in the brain. AD-associated Aß neuropathology begins decades before onset of cognitive symptoms and slowly progresses over the course of the disease. We previously reported discovery of Aß deposition, ß-amyloidopathy, and co-localizing supranuclear cataracts (SNC) in lenses from people with AD, but not other neurodegenerative disorders or normal aging. We confirmed AD-associated Aß molecular pathology in the lens by immunohistopathology, amyloid histochemistry, immunoblot analysis, epitope mapping, immunogold electron microscopy, quantitative immunoassays, and tryptic digest mass spectrometry peptide sequencing. Ultrastructural analysis revealed that AD-associated Aß deposits in AD lenses localize as electron-dense microaggregates in the cytoplasm of supranuclear (deep cortex) fiber cells. These Aß microaggregates also contain αB-crystallin and scatter light, thus linking Aß pathology and SNC phenotype expression in the lenses of people with AD. Subsequent research identified Aß lens pathology as the molecular origin of the distinctive cataracts associated with Down syndrome (DS, trisomy 21), a chromosomal disorder invariantly associated with early-onset Aß accumulation and Aß amyloidopathy in the brain. Investigation of 1249 participants in the Framingham Eye Study found that AD-associated quantitative traits in brain and lens are co-heritable. Moreover, AD-associated lens traits preceded MRI brain traits and cognitive deficits by a decade or more and predicted future AD. A genome-wide association study of bivariate outcomes in the same subjects identified a new AD risk factor locus in the CTNND2 gene encoding δ-catenin, a protein that modulates Aß production in brain and lens. Here we report identification of AD-related human Aß (hAß) lens pathology and age-dependent SNC phenotype expression in the Tg2576 transgenic mouse model of AD. Tg2576 mice express Swedish mutant human amyloid precursor protein (APP-Swe), accumulate hAß peptides and amyloid pathology in the brain, and exhibit cognitive deficits that slowly progress with increasing age. We found that Tg2576 trangenic (Tg+) mice, but not non-transgenic (Tg-) control mice, also express human APP, accumulate hAß peptides, and develop hAß molecular and ultrastructural pathologies in the lens. Tg2576 Tg+ mice exhibit age-dependent Aß supranuclear lens opacification that recapitulates lens pathology and SNC phenotype expression in human AD. In addition, we detected hAß in conditioned medium from lens explant cultures prepared from Tg+ mice, but not Tg- control mice, a finding consistent with constitutive hAß generation in the lens. In vitro studies showed that hAß promoted mouse lens protein aggregation detected by quasi-elastic light scattering (QLS) spectroscopy. These results support mechanistic (genotype-phenotype) linkage between Aß pathology and AD-related phenotypes in lens and brain. Collectively, our findings identify Aß pathology as the shared molecular etiology of two age-dependent AD-related cataracts associated with two human diseases (AD, DS) and homologous murine cataracts in the Tg2576 transgenic mouse model of AD. These results represent the first evidence of AD-related Aß pathology outside the brain and point to lens Aß as an optically-accessible AD biomarker for early detection and longitudinal monitoring of this devastating neurodegenerative disease.

Quantifying Uncertainties in Sequential Chemical Extraction of Soil Phosphorus Using XANES Spectroscopy.

Sequential chemical extraction has been widely used to study soil phosphorus (P) dynamics and inform nutrient management, but its efficacy for assigning P into biologically meaningful pools remains unknown. Here, we evaluated the accuracy of the modified Hedley extraction scheme using P K-edge X-ray absorption near-edge structure (XANES) spectroscopy for nine carbonate-free soil samples with diverse chemical and mineralogical properties resulting from different degrees of soil development. For most samples, the extraction markedly overestimated the pool size of calcium-bound P (Ca-P, extracted by 1 M HCl) due to (1) P redistribution during the alkaline extractions (0.5 M NaHCO3 and then 0.1 M NaOH), creating new Ca-P via formation of Ca phosphates between NaOH-desorbed phosphate and exchangeable Ca2+ and/or (2) dissolution of poorly crystalline Fe and Al oxides by 1 M HCl, releasing P occluded by these oxides into solution. The first mechanism may occur in soils rich in well-crystallized minerals and exchangeable Ca2+ regardless of the presence or absence of CaCO3, whereas the second mechanism likely operates in soils rich in poorly crystalline Fe and Al minerals. The overestimation of Ca-P simultaneously caused underestimation of the pools extracted by the alkaline solutions. Our findings identify key edaphic parameters that remarkably influenced the extractions, which will strengthen our understanding of soil P dynamics using this widely accepted procedure.

Nitrogen dynamics along a climate gradient on geologically old substrate, Kaua'i, Hawai'i.

We evaluated N dynamics on a climate gradient on old (> 4 million year) basaltic substrate on the Island of Kaua'i, Hawai'i, to evaluate the utility of pedogenic thresholds and soil process domains for understanding N cycling in terrestrial ecosystems. Studies of nitrogen dynamics on the climate gradient on a younger basaltic substrate (~ 150,000 year) had found a good match between soil process domains and N cycling processes. Here we measured net N mineralization and nitrification by incubation, and δ15N of total soil N, to determine whether the soil process domains on the older gradient were equally useful for interpreting N cycling and thereby to explore the general utility of the approach. Net N mineralization varied from 0 to 1.7 mg kg-1 d-1 across the old Kaua'i gradient, and δ15N varied from + 3 to + 11 ο/οο, both ranges similar to those on the younger substrate. However, while the pattern of variation with climate was similar for δ15N, the highest rates of mineralization on the old gradient occurred where forests were dominated by the native N fixer Acacia koa. This occurred in sites wetter than the process domain associated with high net N mineralization on the gradient on younger substrate. We conclude that soil process domains based on rock-derived nutrients are not always useful for evaluating N dynamics, especially where the distribution of biological N fixers is controlled by factors other than rock-derived nutrients.

Establishing an allied health professional delivered selective laser trabeculoplasty service in Scotland.

PURPOSE: To describe the process of establishing a selective laser trabeculoplasty (SLT) service delivered by experienced allied health professionals (AHP) in a Scottish NHS Hospital Eye Service, and assess the safety and efficacy in comparison with SLT performed by ophthalmologists. METHODS: A training scheme for AHPs who were experienced in extended roles within the glaucoma service was developed, consisting of supervised training by a consultant ophthalmologist specialising in glaucoma leading to the AHPs independently delivering SLT. A prospective audit of consecutive SLT procedures performed by AHPs between November 2015 and April 2017 was performed. Data were analysed and compared to a previous intradepartmental audit of SLT performed by ophthalmologists (consultants and trainees). RESULTS: A total of 325 eyes of 208 patients underwent SLT, of which 117 patients had bilateral SLT in a single session. The overall rate of complications was 3.9%, however these were minor and/or self-limiting (this compared to a 3.8% complication rate in the ophthalmologist delivered SLT series). The rate of intraocular pressure (IOP) spike was 0.3%, compared to 1.4% in the ophthalmologist delivered SLT series. Mean IOP at listing was 20.9 ± 5.1 mmHg, 17.3 ± 4.5 mmHg at 3 months post SLT and 17.6 ± 3.7 mmHg at 12 months-a median reduction of 16.7% at 3 months and 17.4% at 12 months. There was no statistically significant difference between the percentage reduction in IOP in the AHP and ophthalmologist delivered SLT groups at 3 or 12 months. CONCLUSIONS: This is the first service of its kind in Scotland and the outcomes of this study demonstrate that the AHP delivered SLT service is at least as safe as the previous ophthalmologist delivered SLT service. The data demonstrate a similar efficacy between AHP and ophthalmologist delivered SLT. In the face of increasing demand and workload, this is a practical model in service commissioning to free up medical clinicians for more complex glaucoma management.

Pedothem carbonates reveal anomalous North American atmospheric circulation 70,000-55,000 years ago.

Our understanding of climatic conditions, and therefore forcing factors, in North America during the past two glacial cycles is limited in part by the scarcity of long, well-dated, continuous paleoclimate records. Here, we present the first, to our knowledge, continuous, millennial-resolution paleoclimate proxy record derived from millimeter-thick pedogenic carbonate clast coatings (pedothems), which are widely distributed in semiarid to arid regions worldwide. Our new multiisotope pedothem record from the Wind River Basin in Wyoming confirms a previously hypothesized period of increased transport of Gulf of Mexico moisture northward into the continental interior from 70,000 to 55,000 years ago based on oxygen and carbon isotopes determined by ion microprobe and uranium isotopes and U-Th dating by laser ablation inductively coupled plasma mass spectrometry. This pronounced meridional moisture transport, which contrasts with the dominant zonal transport of Pacific moisture into the North American interior by westerly winds before and after 70,000-55,000 years ago, may have resulted from a persistent anticyclone developed above the North American ice sheet during Marine Isotope Stage 4. We conclude that pedothems, when analyzed using microanalytical techniques, can provide high-resolution paleoclimate records that may open new avenues into understanding past terrestrial climates in regions where paleoclimate records are not otherwise available. When pedothem paleoclimate records are combined with existing records they will add complimentary soil-based perspectives on paleoclimate conditions.

Variation in Rapa Nui (Easter Island) land use indicates production and population peaks prior to European contact.

Many researchers believe that prehistoric Rapa Nui society collapsed because of centuries of unchecked population growth within a fragile environment. Recently, the notion of societal collapse has been questioned with the suggestion that extreme societal and demographic change occurred only after European contact in AD 1722. Establishing the veracity of demographic dynamics has been hindered by the lack of empirical evidence and the inability to establish a precise chronological framework. We use chronometric dates from hydrated obsidian artifacts recovered from habitation sites in regional study areas to evaluate regional land-use within Rapa Nui. The analysis suggests region-specific dynamics including precontact land use decline in some near-coastal and upland areas and postcontact increases and subsequent declines in other coastal locations. These temporal land-use patterns correlate with rainfall variation and soil quality, with poorer environmental locations declining earlier. This analysis confirms that the intensity of land use decreased substantially in some areas of the island before European contact.

Controls of nitrogen cycling evaluated along a well-characterized climate gradient.

The supply of nitrogen (N) constrains primary productivity in many ecosystems, raising the question "what controls the availability and cycling of N"? As a step toward answering this question, we evaluated N cycling processes and aspects of their regulation on a climate gradient on Kohala Volcano, Hawaii, USA. The gradient extends from sites receiving <300 mm/yr of rain to those receiving >3,000 mm/yr, and the pedology and dynamics of rock-derived nutrients in soils on the gradient are well understood. In particular, there is a soil process domain at intermediate rainfall within which ongoing weathering and biological uplift have enriched total and available pools of rock-derived nutrients substantially; sites at higher rainfall than this domain are acid and infertile as a consequence of depletion of rock-derived nutrients, while sites at lower rainfall are unproductive and subject to wind erosion. We found elevated rates of potential net N mineralization in the domain where rock-derived nutrients are enriched. Higher-rainfall sites have low rates of potential net N mineralization and high rates of microbial N immobilization, despite relatively high rates of gross N mineralization. Lower-rainfall sites have moderately low potential net N mineralization, relatively low rates of gross N mineralization, and rates of microbial N immobilization sufficient to sequester almost all the mineral N produced. Bulk soil δ15 N also varied along the gradient, from +4‰ at high rainfall sites to +14‰ at low rainfall sites, indicating differences in the sources and dynamics of soil N. Our analysis shows that there is a strong association between N cycling and soil process domains that are defined using soil characteristics independent of N along this gradient, and that short-term controls of N cycling can be understood in terms of the supply of and demand for N.

Controls on carbon storage and weathering in volcanic soils across a high-elevation climate gradient on Mauna Kea, Hawaii.

Volcanic ash soils retain the largest and most persistent soil carbon pools of any ecosystem. However, the mechanisms governing soil carbon accumulation and weathering during initial phases of ecosystem development are not well understood. We examined soil organic matter dynamics and soil development across a high-altitude (3,560-3,030 m) 20-kyr climate gradient on Mauna Kea in Hawaii. Four elevation sites were selected (~250-500 mm rainfall), which range from sparsely vegetated to sites that contain a mix of shrubs and grasses. At each site, two or three pits were dug and major diagnostic horizons down to bedrock (intact lava) were sampled. Soils were analyzed for particle size, organic C and N, soil pH, exchangeable cations, base saturation, NaF pH, phosphorous sorption, and major elements. Mass loss and pedogenic metal accumulation (hydroxlamine Fe, Al, and Si extractions) were used to measure extent of weathering, leaching, changes in soil mineralogy and carbon accumulation. Reactive-phase (SRO) minerals show a general trend of increasing abundance with increasing rainfall. However carbon accumulation patterns across the climate gradient are largely decoupled from these trends. The results suggest that after 20 kyr, pedogenic processes have altered the nature and composition of the volcanic ash such that it is capable of retaining soil C even where organic acid influences from plant material and leaching from rainfall are severely limited. Carbon storage comparisons with lower-elevation soils on Mauna Kea and other moist mesic (2,500 mm rainfall) sites on Hawaii suggest that these soils have reached only between 1% and 15% of their capacity to retain carbon. Our results suggest that, after 20 kyr in low rainfall and a cold climate, weathering was decoupled from soil carbon accumulation patterns and the associated influence of vegetation on soil development. Overall, we conclude that the rate of carbon supply to the subsoil (driven by coupling of rainfall above ground plant production) is a governing factor of forms and amount of soil organic matter accumulation, while soil mineralogy remained relatively uniform.

Randomized controlled double-blind trial of optimal dose methylphenidate in children and adolescents with severe attention deficit hyperactivity disorder and intellectual disability.

BACKGROUND: Attention deficit hyperactivity disorder is increased in children with intellectual disability. Previous research has suggested stimulants are less effective than in typically developing children but no studies have titrated medication for individual optimal dosing or tested the effects for longer than 4 weeks. METHOD: One hundred and twenty two drug-free children aged 7-15 with hyperkinetic disorder and IQ 30-69 were recruited to a double-blind, placebo-controlled trial that randomized participants using minimization by probability, stratified by referral source and IQ level in a one to one ratio. Methylphenidate was compared with placebo. Dose titration comprised at least 1 week each of low (0.5 mg/kg/day), medium (1.0 mg/kg/day) and high dose (1.5 mg/kg/day). Parent and teacher Attention deficit hyperactivity disorder (ADHD) index of the Conners Rating Scale-Short Version at 16 weeks provided the primary outcome measures. Clinical response was determined with the Clinical Global Impressions scale (CGI-I). Adverse effects were evaluated by a parent-rated questionnaire, weight, pulse and blood pressure. Analyses were by intention to treat. TRIAL REGISTRATION: ISRCTN 68384912. RESULTS: Methylphenidate was superior to placebo with effect sizes of 0.39 [95% confidence intervals (CIs) 0.09, 0.70] and 0.52 (95% CIs 0.23, 0.82) for the parent and teacher Conners ADHD index. Four (7%) children on placebo versus 24 (40%) of those on methylphenidate were judged improved or much improved on the CGI. IQ and autistic symptoms did not affect treatment efficacy. Active medication was associated with sleep difficulty, loss of appetite and weight loss but there were no significant differences in pulse or blood pressure. CONCLUSIONS: Optimal dosing of methylphenidate is practical and effective in some children with hyperkinetic disorder and intellectual disability. Adverse effects typical of methylphenidate were seen and medication use may require close monitoring in this vulnerable group.

When Is the Optimum Radiological Response to Proton Beam Therapy in Uveal Melanoma?

Introduction: Proton beam therapy (PBT) is an effective treatment option for uveal melanomas. Following treatment, it may take many months for the tumour to respond and it may initially enlarge. We reviewed our PBT patients to determine when they showed a radiological response to treatment. Methods: Patients undergoing PBT for ciliary body or choroidal melanomas between 2008 and 2018 were included. Data were collected on patient demographics, treatments before and after PBT and survival. All ultrasound investigations prior and since PBT were reviewed and tumour volume calculated using a validated formula for a half-ellipsoid shape. Results: 193 patients were analysed, 169 with choroidal and 24 with ciliary body melanomas. 31.6% patients had other treatment prior to PBT. At a mean of 8 months post-PBT, 64.7% of patients had a reduced tumour volume with 20.2% having larger tumours. At a mean of 15 months post-treatment, these figures were 67.8% and 10.3%. 18.1% of patients had an enucleation during the study period. The earliest responses were seen at 2 months, the latest at 32 months post-treatment. 5-year melanoma-specific survival was 82.3%. Conclusions: In our study, by 6 months post-PBT, a majority of patients show a reduction in tumour volume. Of those that do not, many respond in the next 6 months and a response may be seen up to 32 months after treatment. Patients may need to be monitored for up to 32 months to see a final response to PBT treatment.

Understanding soil selenium accumulation and bioavailability through size resolved and elemental characterization of soil extracts.

Dietary deficiency of selenium is a global health threat related to low selenium concentrations in crops. Despite the chemical similarity of selenium to the two more abundantly studied elements sulfur and arsenic, the understanding of its accumulation in soils and availability for plants is limited. The lack of understanding of soil selenium cycling is largely due to the unavailability of methods to characterize selenium species in soils, especially the organic ones. Here we develop a size-resolved multi-elemental method using liquid chromatography and elemental mass spectrometry, which enables an advanced characterization of selenium, sulfur, and arsenic species in soil extracts. We apply the analytical approach to soils sampled along the Kohala rainfall gradient on Big Island (Hawaii), which cover a large range of organic carbon and (oxy)hydroxides contents. Similarly to sulfur but contrarily to arsenic, a large fraction of selenium is found associated with organic matter in these soils. However, while sulfur and arsenic are predominantly found as oxyanions in water extracts, selenium mainly exists as small hydrophilic organic compounds. Combining Kohala soil speciation data with concentrations in parent rock and plants further suggests that selenium association with organic matter limits its mobility in soils and availability for plants.

Biological control of terrestrial silica cycling and export fluxes to watersheds.

Silicon has a crucial role in many biogeochemical processes--for example, as a nutrient for marine and terrestrial biota, in buffering soil acidification and in the regulation of atmospheric carbon dioxide. Traditionally, silica fluxes to soil solutions and stream waters are thought to be controlled by the weathering and subsequent dissolution of silicate minerals. Rates of mineral dissolution can be enhanced by biological processes. But plants also take up considerable quantities of silica from soil solution, which is recycled into the soil from falling litter in a separate soil-plant silica cycle that can be significant in comparison with weathering input and hydrologic output. Here we analyse soil water in basaltic soils across the Hawaiian islands to assess the relative contributions of weathering and biogenic silica cycling by using the distinct signatures of the two processes in germanium/silicon ratios. Our data imply that most of the silica released to Hawaiian stream water has passed through the biogenic silica pool, whereas direct mineral-water reactions account for a smaller fraction of the stream silica flux. We expect that other systems exhibiting strong Si depletion of the mineral soils and/or high Si uptake rates by biomass will also have strong biological control on silica cycling and export.

Terrestrial phosphorus limitation: mechanisms, implications, and nitrogen-phosphorus interactions.

Nutrient limitation to primary productivity and other biological processes is widespread in terrestrial ecosystems, and nitrogen (N) and phosphorus (P) are the most common limiting elements, both individually and in combination. Mechanisms that drive P limitation, and their interactions with the N cycle, have received less attention than mechanisms causing N limitation. We identify and discuss six mechanisms that could drive P limitation in terrestrial ecosystems. The best known of these is depletion-driven limitation, in which accumulated P losses during long-term soil and ecosystem development contribute to what Walker and Syers termed a "terminal steady state" of profound P depletion and limitation. The other mechanisms are soil barriers that prevent access to P; transactional limitation, in which weathering of P-containing minerals does not keep pace with the supply of other resources; low-P parent materials; P sinks; and anthropogenic changes that increase the supply of other resources (often N) relative to P. We distinguish proximate nutrient limitation (which occurs where additions of a nutrient stimulate biological processes, especially productivity) from ultimate nutrient limitation (where additions of a nutrient can transform ecosystems). Of the mechanisms that drive P limitation, we suggest that depletion, soil barriers, and low-P parent material often cause ultimate limitation because they control the ecosystem mass balance of P. Similarly, demand-independent losses and constraints to N fixation can control the ecosystem-level mass balance of N and cause it to be an ultimate limiting nutrient.

Climate and soil-age constraints on nutrient uplift and retention by plants.

Plants and soils represent coevolving components of ecosystems, and while the effects of soils (e.g., nutrient availability) on plants have been extensively documented, the effect of plants on soils has received less attention. Furthermore there has been no systematic investigation of how plant effects vary across important ecological gradients in climate or soil age, which leaves a substantial gap in our understanding of how plant-soil systems develop. In this context, we analyzed changes in nutrient availability and elemental losses from the entire weathering zone at 35 sites arrayed across climatic and soil-age gradients on the island of Hawai'i. The sites are located on three basaltic lava flows (ages 10, 170, and 350 kyr) each of which crosses a precipitation gradient from approximately 500 to 2500 mm/yr. By comparing the loss of nutrient (potassium, phosphorus) and non-nutrient (e.g., sodium) rock-derived elements, we identify a climatic zone at intermediate rainfall where the retention of plant nutrients in the upper soil is most pronounced. We further show that there are several abiotic constraints on plant-driven retention of nutrients. At the dry sites (< or = 750 mm/yr on all three flows), plants slow the loss of nutrients, but the effect (as measured by the difference between K and Na losses) is small, perhaps because of low plant cover and productivity. At intermediate rainfall (750-1400 mm/yr) but negative water balance, plants substantially enrich both nutrient cations and P relative to Na in the surface horizons, an effect that remains strong even after 350 kyr of soil development. In contrast, at high rainfall (> or = 1500 mm/yr) and positive water balance, the effect of plants on nutrient distributions diminishes with soil age as leaching losses overwhelm the uplift and retention of nutrients by plants after 350 kyr of soil development. The effect of plants on soil nutrient distributions can also be mediated by the movement of iron (Fe), and substantial Fe losses at high rainfall on the older flows are highly correlated with P losses. Thus redox-driven redistribution of Fe may place a further abiotic constraint on nutrient retention by plants. In combination, these data indicate that the effects of soil aging on plant uplift and retention of nutrients differ markedly with precipitation, and we view this as a potentially fruitful area for future research.

Landscape-level variation in forest structure and biogeochemistry across a substrate age gradient in Hawaii.

We compared forest canopy heights and nitrogen concentrations in long-term research sites and in 2 x 2 km landscapes surrounding these sites along a substrate age gradient in the Hawaiian Islands. Both remote airborne and ground-based measurements were used to characterize processes that control landscape-level variation in canopy properties. We integrated a waveform light detection and ranging (LiDAR) system, a high-resolution imaging spectrometer, and a global positioning system/inertial measurement unit to provide highly resolved images of ground topography, canopy heights, and canopy nitrogen concentrations (1) within a circle 50 m in radius focused on a long-term study site in the center of each landscape; (2) for the entire 2 x 2 km landscape regardless of land cover; and (3) after stratification, for our target cover class, native-dominated vegetation on constructional geomorphic surfaces throughout each landscape. Remote measurements at all scales yielded the same overall patterns as did ground-based measurements in the long-term sites. The two younger landscapes supported taller trees than did older landscapes, while the two intermediate-aged landscapes had higher canopy nitrogen (N) concentrations than did either young or old landscapes. However, aircraft-based analyses detected substantial variability in canopy characteristics on the landscape level, even within the target cover class. Canopy heights were more heterogeneous on the older landscapes, with coefficients of variation increasing from 23-41% to 69-78% with increasing substrate age. This increasing heterogeneity was associated with a larger patch size of canopy turnover and with dominance of most secondary successional stands by the mat-forming fern Dicranopteris linearis in the older landscapes.

Sources of nutrients to windward agricultural systems in pre-contact Hawai'i.

Prior to European contact in 1778, Hawaiians developed intensive irrigated pondfield agricultural systems in windward Kohala, Hawai'i. We evaluated three potential sources of nutrients to windward systems that could have sustained intensive agriculture: (1) in situ weathering of primary and secondary minerals in upland soils; (2) rejuvenation of the supply of rock-derived nutrients on eroded slopes and in alluvium; and (3) transport of rock-derived nutrients to crops via irrigation water. Our results show that most windward soils are infertile and suggest that weathering of minerals within upland soils was insufficient to sustain intensive agriculture without substantial cultural inputs. Erosion enhances weathering and so increases nutrient supply, with soils of the largest alluvial valleys (>200 m deep) retaining 37% of calcium from parent material (compared to 2% in upland sites). However, soils of smaller valleys that also supported pre-contact agricultural systems are substantially less enriched. Isotopic 87Sr/86Sr analyses of stream water demonstrate that at low to moderate stream flow over 90% of dissolved strontium derives from weathering of basalt rather than deposition of atmospheric sources; most other dissolved cations also derive from basalt weathering. We calculate that irrigation water could have supplied approximately 200 kg ha(-1) yr(-1) of calcium to pondfield systems, nearly 100 times more than was supplied by weathering in soils on stable geomorphic surfaces. In effect, irrigation waters brought nutrients from rocks to the windward crops.

Quantitative Analysis of Pedogenic Thresholds and Domains in Volcanic Soils.

Pedogenic thresholds describe where soil properties or processes change in an abrupt/nonlinear fashion in response to small changes in environmental forcing. Contrastingly, soil process domains refer to the space between thresholds where soil properties are either unchanged, or change gradually, across a broad range of environmental forcing. Here, we test quantitatively for the presence of thresholds in patterns of soil properties across a climatic gradient on soils developed from ~20 ky old basaltic substrate on the Island of Hawai'i. From multiple soil properties, we quantitatively identified a threshold at ~750 mm/y of water balance (precipitation minus potential evapotranspiration), delineating the upper water balance boundary of soil fertility in these soils. From the threshold in the ratio of exchangeable Ca to total Ca we identified the lower water balance boundary of soil fertility in these soils at -1000 mm/y, however this threshold was qualitatively described as it lies near the limit of the climate gradient data where the statistical approach can not be applied. These two results represent the first time that pedogenic thresholds have been identified using statistically rigorous methods and the limitations of said methods, respectively. Comparing the 20 ky soils to soils that developed on basaltic substrates of 1.2 ky, 7.5 ky, 150 ky, and 4100 ky in a time-climate matrix, we found that our quantitative analysis supports previous qualitatively identified thresholds in the soils developed from older substrates. We also identified the 20 ky as the transition from kinetic to supply limitation for plant nutrients in soil in this system.

Combining spectroscopic and isotopic techniques gives a dynamic view of phosphorus cycling in soil.

Current understanding of phosphorus (P) cycling in soils can be enhanced by integrating previously discrete findings concerning P speciation, exchange kinetics, and the underlying biological and geochemical processes. Here, we combine sequential extraction with P K-edge X-ray absorption spectroscopy and isotopic methods (33P and 18O in phosphate) to characterize P cycling on a climatic gradient in Hawaii. We link P pools to P species and estimate the turnover times for commonly considered P pools. Dissolved P turned over in seconds, resin-extractable P in minutes, NaOH-extractable inorganic P in weeks to months, and HCl-extractable P in years to millennia. Furthermore, we show that in arid-zone soils, some primary mineral P remains even after 150 ky of soil development, whereas in humid-zone soils of the same age, all P in all pools has been biologically cycled. The integrative information we provide makes possible a more dynamic, process-oriented conceptual model of P cycling in soils.