Distribution and Abundance of Arsenic in the Soils and Sediments of O‘ahu,Hawai‘i

Lack of high-spatial-resolution soil and sediment arsenic data for Hawai‘i has generated substantial disagreement between researchers and regulators regarding the magnitude of natural levels of arsenic in Hawai‘i and rendered difficult the defining of areas of anthropogenically elevated arsenic. Our earlier research into the occurrence of arsenic in terrestrial and marine environments revealed widely disparate concentrations of arsenic with no apparent spatial pattern. To better understand the distribution and abundance of arsenic in soils and sediments of O‘ahu, we collected an additional 64 samples at locations chosen to represent different environments with varying degrees of human impact. We found surface arsenic values that ranged from 0.28 to 740 ppm with a median concentration of 8.1 ppm, which is above the global median of 5 ppm and US soil median of 5.2 ppm. Higher concentrations of arsenic (up to 913 ppm) were encountered at depth in soil cores. The median arsenic in streambed sediments from one of our earlier studies of 6.1 ppm was comparable to the conterminous US median of 6.3 ppm; however, we encountered arsenic concentrations as high as 43.9 ppm (median = 8.60 ppm, n = 75) in marine sediments in recent work off the leeward coast of O‘ahu. Overall, arsenic in the soils and sediments of O‘ahu is elevated relative to world and national values, but there still is no readily discernible pattern in the distribution of arsenic to explain these elevated values.     

Experimental analysis of arsenic precipitation during microbial sulfate and iron reduction in model aquifer sediment reactors

Microbial SO₄²⁻ reduction limits accumulation of aqueous As in reducing aquifers where the sulfide that is produced forms minerals that sequester As. We examined the potential for As partitioning into As- and Fe-sulfide minerals in anaerobic, semi-continuous flow bioreactors inoculated with 0.5% (g mL⁻¹) fine-grained alluvial aquifer sediment. A fluid residence time of three weeks was maintained over a ca. 300-d incubation period by replacing one-third of the aqueous phase volume of the reactors with fresh medium every seven days. The medium had a composition comparable to natural As-contaminated groundwater with slightly basic pH (7.3) and 7.5 μM aqueous As(V) and also contained 0.8 mM acetate to stimulate microbial activity. Medium was delivered to a reactor system with and without 10 mmol L⁻¹ synthetic goethite (α-FeOOH). In both reactors, influent As(V) was almost completely reduced to As(III). Pure As-sulfide minerals did not form in the Fe-limited reactor. Realgar (As₄S₄) and As₂S₃(am) were undersaturated throughout the experiment. Orpiment (As₂S₃) was saturated while sulfide content was low (∼50 to 150 μM), but precipitation was likely limited by slow kinetics. Reaction-path modeling suggests that, even if these minerals had formed, the dissolved As content of the reactor would have remained at hazardous levels. Mackinawite (Fe_1 + xS; x ? 0.07) formed readily in the Fe-bearing reactor and held dissolved sulfide at levels below saturation for orpiment and realgar. The mackinawite sequestered little As (<0.1 wt.%), however, and aqueous As accumulated to levels above the influent concentration as microbial Fe(III) reduction consumed goethite and mobilized adsorbed As. A relatively small amount of pyrite (FeS₂) and greigite (Fe₃S₄) formed in the Fe-bearing reactor when we injected a polysulfide solution (Na₂S₄) to a final concentration of 0.5 mM after 216, 230, 279, and 286 days. The pyrite, and to a lesser extent the greigite, that formed did sequester As from solution, containing 0.84 and 0.23 wt.% As on average, respectively. Our results suggest that As precipitation during Fe-sulfide formation in nature occurs mainly in conjunction with pyrite formation. Our findings imply that the effectiveness of stimulating microbial SO₄²⁻ reduction to remediate As contamination may be limited by the rate and extent of pyrite formation and the solubility of As-sulfides.     

Dynamics of epiphytic photoautotrophs and heterotrophs inZostera marina (eelgrass) microcosms: Responses to nutrient enrichment and grazing

The combined effects of nutrient enrichment and grazing by isopods and amphipods on abundances of seagrass epiphytes were tested inZostera marina L. (eelgrass) microcosms. Using epifluorescence microscopy, densities of epiphytic diatoms, cyanobacteria, heterotrophic flagellates, and heterotrophic bacteria were enumerated after 1 mo and 2 mo of treatment. In general, numbers of diatoms decreased, in the presence of grazers and showed little response to nutrient enrichment, whereas numbers of cyanobacteria increased with nutrient enrichment and showed little response to grazing. Thus, macrofaunal grazing maintained a photoautotrophic community domainated by cyanobacteria, particularly under nutrient enriched conditions. Following 2 mo of treatment, dense macroalgal growth under nutrient-enriched conditins with grazers absent appeared to limit populations of both epiphytic autotrophs. Patterns of abundance of heterotrophic bacteria suggested that the original bacteria population was nutrient limited. Bacteria populations may have been limited by organic carbon supplies at the end of the experiment. Abundances of heterotrophic flagellates and bacteria were strongly correlated on both sampling dates. Results suggest that heterotrophic flagellates might serve as a link between heterotrophic bacterial production and higher trophic levels in seagrass epiphyte food webs.     

Natural disasters as the end of the insurance industry? Scalar competitive strategies, Alternative Risk Transfers, and the economic crisis

The aftermath of Hurricane Katrina has piqued interest in the insurance industry, and this scrutiny has led to assumptions that the industry has become unstable and unprofitable with the increased incidence of disasters in highly-insured regions of the world. This paper challenges that assumption by arguing that the insurance industry has responded by spreading risk through scaled and networked recovery schemes. We found that because of competitive strategies of risk-spreading and displacement arrangements, the industry has actually profited as a whole. Regional insurance companies have always relied on the higher financial scales of the reinsurance industry in Munich, Zurich, and London. But with claims reaching into the billions of dollars, the reinsurance industry itself has raised premiums, spread risk farther afield, and jumped scale by spreading risk to futures markets called Alternative Risk Transfers (ARTs). However, the recession beginning in 2008 has called into question the viability of using futures markets as insurance. It is shown through a media analysis of four major business publications (The Economist, The New York Times, The Financial Times and The Wall Street Journal) how the industry responded to the costs of the 2004, 2005, and 2006 hurricane seasons. Because geography is rather new to this literature, this paper also offers a broad review of the insurance industry.     

A Leaky-Conduit Model of Transient Flow in Karstic Aquifers

Karst Flow Model (KFM) simulates transient flow in an unconfined karstic aquifer having a well-developed conduit system. KFM treats the springshed as a two-dimensional porous matrix containing a triangulated irregular network of leaky conduits. The number and location of conduits can be specified arbitrarily, perhaps using field information as a guide, or generated automatically. Conduit networks can be tree-like or braided. Rainwater that has infiltrated down from the surface leaks into the conduits from the adjacent porous matrix at a rate dictated by Darcy’s law, then flows turbulently to the spring via the conduits. KFM is calibrated using the known steady state; geometry and recharge determine the steady fluxes in the conduits, and the head distribution determines conduit gradients and sizes. Spring flow can vary with time due to spatially and temporally variable recharge and due to prescribed variations in the elevation of the spring. KFM is illustrated by four examples run on a test aquifer consisting of 27 nodes, 42 elements, and 26 conduits. Three examples (drought, uniform rainstorm, storm-water input to one element) are simulations, while the fourth uses data from a spring-basin flooding event. The qualitative fit between the predicted and observed spring discharge in the fourth example provides support of the hypothesis that the dynamic behavior of a karst conduit system is an emergent property of a self-organized system, largely independent of the locations and properties of individual conduits.     

Magmatic-to-hydrothermal crystallization in the W–Sn mineralized Mole Granite (NSW, Australia): Part I: Crystallization of zircon and REE-phosphates over three million years—a geochemical and U–Pb geochronological study

Zircon, monazite and xenotime crystallized over a temperature interval of several hundred degrees at the magmatic to hydrothermal transition of the Sn and W mineralized Mole Granite. Magmatic zircon and monazite, thought to have crystallized from hydrous silicate melt, were dated by conventional U–Pb techniques at an age of 247.6 ± 0.4 and 247.7 ± 0.5 Ma, respectively. Xenotime occurring in hydrothermal quartz is found to be significantly younger at 246.2 ± 0.5 Ma and is interpreted to represent hydrothermal growth. From associated fluid inclusions it is concluded that it precipitated from a hydrothermal brine ≤ 600 °C, which is below the accepted closure temperature for U–Pb in this mineral. These data are compatible with a two-stage crystallization process: precipitation of zircon and monazite as magmatic liquidus phases in deep crustal magma followed by complete crystallization and intimately associated Sn–W mineralization after intrusion of the shallow, sill-like body of the Mole Granite. Later hydrothermal formation of monazite in a biotite–fluorite–topaz reaction rim around a mineralized vein was dated at 244.4 ± 1.4 Ma, which distinctly postdates the Mole Granite and is possibly related to a younger hidden intrusion and its hydrothermal fluid system.

Obtaining precise age data for magmatic and hydrothermal minerals of the Mole Granite is hampered by uncertainties introduced by different corrections required for multiple highly radiogenic minerals crystallising from evolved hydrous granites, including ²³⁰Th disequilibrium due to Th/U fractionation during monazite and possibly xenotime crystallization, variable Th/U ratios of the fluids from which xenotime was precipitating, elevated contents of common lead, and post-crystallization lead loss in zircon, enhanced by the fluid-saturated environment. The data imply that monazite can also survive as a liquidus phase in protracted magmatic systems over periods of 10⁶ years. The outlined model is in agreement with prominent chemical core-rim variation of the zircon.     

Nutrient Inputs, Phytoplankton Response, and CO2 Variations in a Semi-Enclosed Subtropical Embayment, Kaneohe Bay, Hawaii

The marine shelf areas in subtropical and tropical regions represent only 35% of the total shelf areas globally, but receive a disproportionately large amount of water (65%) and sediment (58%) discharges that enter such environments. Small rivers and/or streams that drain the mountainous areas in these climatic zones deliver the majority of the sediment and nutrient inputs to these narrow shelf environments; such inputs often occur as discrete, episodic introductions associated with storm events. To gain insight into the linked biogeochemical behavior of subtropical/tropical mountainous watershed-coastal ocean ecosystems, this work describes the use of a buoy system to monitor autonomously water quality responses to land-derived nutrient inputs and physical forcing associated with local storm events in the coastal ocean of southern Kaneohe Bay, Oahu, Hawaii, USA. The data represent 2.5 years of near-real time observations at a fixed station, collected concurrently with spatially distributed synoptic sampling over larger sections of Kaneohe Bay. Storm events cause most of the fluvial nutrient, particulate, and dissolved organic carbon inputs to Kaneohe Bay. Nutrient loadings from direct rainfall and/or terrestrial runoff produce an immediate increase in the N:P ratio of bay waters up to values of 48 and drive phytoplankton biomass growth. Rapid uptake of such nutrient subsidies by phytoplankton causes rapid declines of N levels, return to N-limited conditions, and subsequent decline of phytoplankton biomass over timescales ranging from a few days to several weeks, depending on conditions and proximity to the sources of runoff. The enhanced productivity may promote the drawing down of pCO₂ and lowering of surface water column carbonate saturation states, and in some events, a temporary shift from N to P limitation. The productivity-driven CO₂ drawdown may temporarily lead to air-to-sea transfer of atmospheric CO₂ in a system that is on an annual basis a source of CO₂ to the atmosphere due to calcification and perhaps heterotrophy. Storms may also strongly affect proximal coastal zone pCO₂ and hence carbonate saturation state due to river runoff flushing out high pCO₂ soil and ground waters. Mixing of the CO₂-charged water with seawater causes a salting out effect that releases CO₂ to the atmosphere. Many subtropical and tropical systems throughout the Pacific region are similar to Kaneohe Bay, and our work provides an important indication of the variability and range of CO₂ dynamics that are likely to exist elsewhere. Such variability must be taken into account in any analysis of the direction and magnitude of the air?Csea CO₂ exchange for the integrated coastal ocean, proximal and distal. It cannot be overemphasized that this research illustrates several examples of how high frequency sampling by a moored autonomous system can provide details about ecosystem responses to stochastic atmospheric forcing that are commonly missed by traditional synoptic observational approaches. Finally, the work exemplifies the utility of combining synoptic sampling and real-time autonomous observations to elucidate the biogeochemical and physical responses of coastal subtropical/tropical coral reef ecosystems to climatic perturbations.