Photobleaching of chromophoric dissolved organic matter (CDOM) in rainwater

Significant photodegradation of chromophoric dissolved organic matter (CDOM) in rainwater was observed after exposure to simulated sunlight. Fluorescence excitation emission spectra (EEMS) of precipitation revealed the presence of four major peaks all of which degraded upon photolysis with the greatest loss in the region characteristic of marine CDOM. Photobleaching of absorbance also occurred in the wavelength region between 250 and 375 nm with the greatest loss of absorbance in the upper end of the UV-A region near 275 nm. There was a strong positive correlation between absorbance loss and total integrated fluorescence loss suggesting these optical properties and the degree to which they are photobleached in rainwater are directly related. The quantum yield of CDOM photodegradation in rainwater decreased dramatically with increasing wavelength and decreasing energy of incoming radiation with the average quantum yield at 325 nm approximately an order of magnitude greater than at 460 nm. The similarity of photolytic response between rainwater and Cape Fear estuarine CDOM indicates that some fraction of the compounds that make up rainwater CDOM may be derived from surface sources and/or that the processes that produce or modify humic-like substances in the atmosphere result in similar types of compounds as non-atmospheric processes.     

Enhancing RUSLE to include runoff‐driven phenomena

RUSLE2 (Revised Universal Soil Loss Equation) is the most recent in the family of Universal Soil Loss Equation (USLE)/RUSLE/RUSLE2 models proven to provide robust estimates of average annual sheet and rill erosion from a wide range of land use, soil, and climatic conditions. RUSLE2's capabilities have been expanded over earlier versions using methods of estimating time‐varying runoff and process‐based sediment transport routines so that it can estimate sediment transport/deposition/delivery on complex hillslopes. In this report we propose and evaluate a method of predicting a series of representative runoff events whose sizes, durations, and timings are estimated from information already in the RUSLE2 database. The methods were derived from analysis of 30‐year simulations using a widely accepted climate generator and runoff model and were validated against additional independent simulations not used in developing the index events, as well as against long‐term measured monthly rainfall/runoff sets. Comparison of measured and RUSLE2‐predicted monthly runoff suggested that the procedures outlined may underestimate plot‐scale runoff during periods of the year with greater than average rainfall intensity, and a modification to improve predictions was developed. In order to illustrate the potential of coupling RUSLE2 with a process‐based channel erosion model, the resulting set of representative storms was used as an input to the channel routines used in Chemicals, Runoff, and Erosion from Agricultural Management Systems (CREAMS) to calculate ephemeral gully erosion. The method was applied to a hypothetical 5‐ha field cropped to cotton in Marshall County, MS, bisected by a potential ephemeral gully having channel slopes ranging from 0·5 to 5% and with hillslopes on both sides of the channel with 5% steepness and 22·1 m length. Results showed the representative storm sequence produced reasonable results in CREAMS indicating that ephemeral gully erosion may be of the same order of magnitude as sheet and rill erosion. Copyright © 2010 John Wiley & Sons, Ltd.     

Streambank dewatering for increased stability

Streambank erosion is often the dominant source of sediment leaving modified watersheds. Mass failure of high, steep banks is one of the most serious forms of streambank erosion. The risk of a given bank experiencing mass failure is a function of bank height, angle, and soil strength, which is governed by soil moisture. Two methods for bank dewatering were tested in adjacent sections of streambank bordering a deeply incised channel in northern Mississippi: a low‐cost pump system and subsurface horizontal drains. Pore water pressures (both positive and negative pressures, or matric suction) were continuously monitored for 2 years at the pumped site, at an adjacent untreated control section, and for 1 year at the site stabilized with horizontal drains. Resulting data were used to calculate a time series of the factor of safety using a computer model. Over the course of two wet seasons, average bank retreats for the control and pumped plots were 0·43 and 0·21 m, respectively. More limited monitoring revealed that the site with passive drains retreated about 0·23 m. At the pumped site pore water pressure was 3–4 kPa lower than at the control site during the most critical periods. Accordingly, computed factors of safety were above the failure threshold at the pumped site, but fell below unity at the control site on 11 occasions over the period of observation. Similarly, the drained site displayed generally lower pore water pressure and higher safety factors except for two events when drains were evidently overwhelmed with the volume of local surface and subsurface flows. These results suggest, but do not prove, that bank dewatering promoted lower rates of bank retreat and higher levels of stability since the three sites had slight differences in soils, geometry and boundary conditions. Initial cost of the dewatering treatments were significantly less than orthodox bank stabilization measures, but operation and maintenance requirements may be greater. Published in 2009 by John Wiley & Sons, Ltd.     

Rainfall–runoff trends in the south‐eastern USA: 1938–2005

An extensive dataset (230 precipitation gauges and 79 stream gauges) was used to analyse rainfall–runoff relationships in 10 subregions of a 482000 km² area in the south‐eastern USA (Maryland, Virginia, North Carolina, South Carolina and Georgia). The average annual rainfall and runoff for this study area between 1938 and 2005 were 1201 and 439 mm, respectively. Average runoff/rainfall ratios during this period varied between 0·24 in the southernmost Coastal Plain subregion to 0·64 in the Blue Ridge Province. Watershed elevation and relief are the principal determinants governing the conversion of rainfall to runoff. Temporal rainfall variation throughout the south‐eastern USA ranges from ～40% above and below normal while the variation for runoff is higher, from ? 75% to + 100%. In any given year there can exist a ± 25–50% error in predicted runoff deviation using the annual rainfall–runoff regression. Fast Fourier Transform and autoregressive spectral analysis revealed dominant cyclicities for rainfall and runoff between 14 and 17 years. Secondary periodicities were typically between 6–7 and 10–12 years. The inferred cyclicity may be related to ENSO and/or Central North Pacific atmospheric phenomena. Mann–Kendall analyses indicate that there were no consistent statistically significant temporal trends with respect to south‐eastern US rainfall and runoff during the study period. The results of U‐tests similarly indicated that rainfall between 1996 and 2005 was not statistically higher or lower than during earlier in the study period. Copyright © 2008 John Wiley & Sons, Ltd.     

Preservation of layered paleodeposits in high-latitude pedestal craters on Mars

An outstanding question in Mars’ climate history is whether or not pedestal craters represent the armored remnants of ice-rich paleodeposits. We address this question using new high-resolution images; in a survey of several hundred high-latitude pedestal craters, we have identified 12 examples in which visible and/or topographically expressed layers are exposed on the marginal scarp of the pedestal. One example, located on the south polar layered deposits, preserves ice-rich layers that have otherwise been completely removed from the polar cap. These observations provide empirical evidence that the pedestal crater formation mechanism is capable of armoring and preserving ice-rich layered paleodeposits. Although layered exposures have not yet been observed in mid-latitude pedestal craters, high-latitude instances of discontinuous, partially covered layers suggest that layers can be readily concealed, likely through mantling and/or mass wasting processes along the marginal scarp. This interpretation is supported by the observation that high-latitude pedestals with exposed layers along their margins are, on average, taller than mid-latitude examples, and have larger, steeper marginal scarps, which may help to maintain layer exposures. These observations favor the interpretation that mid- to high-latitude pedestal craters represent the armored remnants of ice- and dust-rich paleodeposits, which occurred transiently due to changes in the climate regime. Preservation of fine-scale layering of ice and dust at these latitudes implies that the climate change did not involve regional melting conditions.     

Statistical tests of chondrule sorting

Abstract– The variation in sizes of chondrules from one chondrite to the next is thought to be due to some sorting process in the early solar nebula. Hypotheses for the sorting process include chondrule sorting by mass and sorting by some aerodynamic mechanism; one such aerodynamic mechanism is the process of turbulent concentration (TC). We present the results of a series of statistical tests of chondrule data from several different chondrites. The data do not clearly distinguish between various options for the sorting parameter, but we find that the data are inconsistent with being drawn from lognormal or (three‐parameter) Weibull distributions in chondrule radius. We also find that all but one of the chondrule data sets tested are consistent with being drawn from the TC distribution.     

Effect of temperature and mass transport on transition metal isotope fractionation during electroplating

Transition metal stable isotope signatures can be useful for tracing both natural and anthropogenic signals in the environment, but only if the mechanisms responsible for fractionation are understood. To investigate isotope fractionations due to electrochemistry (or redox processes), we examine the stable isotope behavior of iron and zinc during the reduction reaction  + 2e⁻ = M_metal as a function of electrochemical driving force, temperature, and time. In all cases light isotopes are preferentially electroplated, following a mass-dependent law. Generally, the extent of fractionation is larger for higher temperatures and lower driving forces, and is roughly insensitive to amount of charge delivered. The maximum fractionations are δ^56/54Fe = −4.0‰ and δ^66/64Zn = −5.5‰, larger than observed fractionations in the natural environment and larger than those predicted due to changes in speciation. All the observed fractionation trends are interpreted in terms of three distinct processes that occur during an electrochemical reaction: mass transport to the electrode, chemical speciation changes adjacent to the electrode, and electron transfer at the electrode. We show that a large isotope effect adjacent the electrode surface arises from the charge-transfer kinetics, but this effect is attenuated in cases where diffusion of ions to the electrode surface becomes the rate-limiting step. Thus while a general increase in fractionation is observed with increasing temperature, this appears to be a result of thermally enhanced mass transport to the reacting interface rather than an isotope effect associated with the charge-transfer kinetics. This study demonstrates that laboratory experiments can successfully distinguish isotopic signatures arising from mass transport, chemical speciation, and electron transfer. Understanding how these processes fractionate metal isotopes under laboratory conditions is the first step towards discovering what role these processes play in fractionating metal isotopes in natural systems.     

Transport of Crustacean Larvae Between a Low-Inflow Estuary and Coastal Waters

The effectiveness of larval behavior in regulating transport between well-mixed, low-inflow estuaries and coastal waters in seasonally arid climates is poorly known. We determined the flux of an assemblage of benthic crustacean larvae relative to physical conditions between a shallow estuary and coastal waters on the upwelling coast of northern California (38°18′N, 123°03′W) from 29 to 31 March 2006. We detected larval behaviors that regulate transport in adjacent coastal waters and other estuaries for only two taxa in the low-inflow estuary, but they were apparent for taxa outside the estuary. Vertical mixing in the shallow estuary may have overwhelmed larvae of some species, or salinity fluctuations may have been too slight to cue tidal vertical migrations. Nevertheless, all larval stages of species that complete development in nearshore coastal waters were present in the estuary, because they remained low in the water column reducing seaward advection or they were readily exchanged between the estuary and open coast by tidal flows. Weak tidal flows and gravitational circulation at the head of the estuary reduced seaward transport during development for species that completed development nearshore, whereas larval release during nocturnal ebb tides enhanced seaward transport for species that develop offshore. Thus, nonselective tidal processes dominated larval transport for most species back and forth between the low-inflow estuary and open coastal waters, whereas in adjacent open coastal waters, larval behavior in the presence of wind-induced shear was more important in regulating migrations between adult and larval habitats along this upwelling coast.     

Resolving mechanisms of toxicity while pursuing ecotoxicological relevance?

In this age of modern biology, aquatic toxicological research has pursued mechanisms of action of toxicants. This has provided potential tools for ecotoxicologic investigations. However, problems of biocomplexity and issues at higher levels of biological organization remain a challenge. In the 1980s and 1990s and continuing to a lesser extent today, organisms residing in highly contaminated field sites or exposed in the laboratory to calibrated concentrations of individual compounds were carefully analyzed for their responses to priority pollutants. Correlation of biochemical and structural analyses in cultured cells and tissues, as well as the in vivo exposures led to the production and application of biomarkers of exposure and effect and to our awareness of genotoxicity and its chronic manifestations, such as neoplasms, in wild fishes. To gain acceptance of these findings in the greater environmental toxicology community, “validation of the model” versus other, better-established often rodent models, was necessary and became a major focus. Resultant biomarkers were applied to heavily contaminated and reference field sites as part of effects assessment and with investigations following large-scale disasters such as oil spills or industrial accidents.

Over the past 15 years, in the laboratory, small aquarium fish models such as medaka (Oryzias latipes), zebrafish (Danio rerio), platyfish (Xiphophorus species), fathead minnow (Pimephales promelas), and sheepshead minnow (Cyprinodon variegatus) were increasingly used establishing mechanisms of toxicants. Today, the same organisms provide reliable information at higher levels of biological organization relevant to ecotoxicology. We review studies resolving mechanisms of toxicity and discuss ways to address biocomplexity, mixtures of contaminants, and the need to relate individual level responses to populations and communities.