Assessment and control of organic and other contaminants associated with the Stardust sample return from comet 81P/Wild 2

Abstract– Numerous potential sources of organic contaminants could have greatly complicated the interpretation of the organic portions of the samples returned from comet 81P/Wild 2 by the Stardust spacecraft. Measures were taken to control and assess potential organic (and other) contaminants during the design, construction, and flight of the spacecraft, and during and after recovery of the sample return capsule. Studies of controls and the returned samples suggest that many of these potential sources did not contribute any significant material to the collectors. In particular, contamination from soils at the recovery site and materials associated with the ablation of the heatshield do not appear to be significant problems. The largest source of concern is associated with the C present in the original aerogel. The relative abundance of this carbon can vary between aerogel tiles and even within individual tiles. This C was fortunately not distributed among a complex mixture of organics, but was instead largely present in a few simple forms (mostly as Si‐CH₃ groups). In most cases, the signature of returned cometary organics can be readily distinguished from contaminants through their different compositions, nonterrestrial isotopic ratios, and/or association with other cometary materials. However, some conversion of the carbon indigenous to the flight aerogel appears to have happened during particle impact, and some open issues remain regarding how this C may be processed into new forms during the hypervelocity impact collection of the comet dust.     

The effects of parent body processes on amino acids in carbonaceous chondrites

Abstract– To investigate the effect of parent body processes on the abundance, distribution, and enantiomeric composition of amino acids in carbonaceous chondrites, the water extracts from nine different powdered CI, CM, and CR carbonaceous chondrites were analyzed for amino acids by ultra performance liquid chromatography‐fluorescence detection and time‐of‐flight mass spectrometry (UPLC‐FD/ToF‐MS). Four aqueously altered type 1 carbonaceous chondrites including Orgueil (CI1), Meteorite Hills (MET) 01070 (CM1), Scott Glacier (SCO) 06043 (CM1), and Grosvenor Mountains (GRO) 95577 (CR1) were analyzed using this technique for the first time. Analyses of these meteorites revealed low levels of two‐ to five‐carbon acyclic amino alkanoic acids with concentrations ranging from approximately 1 to 2,700 parts‐per‐billion (ppb). The type 1 carbonaceous chondrites have a distinct distribution of the five‐carbon (C₅) amino acids with much higher relative abundances of the γ‐ and δ‐amino acids compared to the type 2 and type 3 carbonaceous chondrites, which are dominated by α‐amino acids. Much higher amino acid abundances were found in the CM2 chondrites Murchison, Lonewolf Nunataks (LON) 94102, and Lewis Cliffs (LEW) 90500, the CR2 Elephant Moraine (EET) 92042, and the CR3 Queen Alexandra Range (QUE) 99177. For example, α‐aminoisobutyric acid (α‐AIB) and isovaline were approximately 100 to 1000 times more abundant in the type 2 and 3 chondrites compared to the more aqueously altered type 1 chondrites. Most of the chiral amino acids identified in these meteorites were racemic, indicating an extraterrestrial abiotic origin. However, nonracemic isovaline was observed in the aqueously altered carbonaceous chondrites Murchison, Orgueil, SCO 06043, and GRO 95577 with l ‐isovaline excesses ranging from approximately 11 to 19%, whereas the most pristine, unaltered carbonaceous chondrites analyzed in this study had no detectable l ‐isovaline excesses. These results are consistent with the theory that aqueous alteration played an important role in amplification of small initial left handed isovaline excesses on the parent bodies.     

Agricultural and forested land use impacts on floodplain shallow groundwater temperature regime

Given the importance of groundwater temperature to the biogeochemical health of aquatic ecosystems, a floodplain study was implemented to improve understanding of rural land use impacts on shallow groundwater (SGW) temperature. Study sites included a historic agricultural field (Ag) and bottomland hardwood forest (BHF), each with nine piezometers in an 80 × 80 m grid. Piezometers were equipped with pressure transducers to monitor SGW temperature and level at 30 min intervals during the 2011, 2012, 2013, and 2014 water years. The study is one of the first to utilize long‐term, continuous, automated, in situ monitoring to investigate rural land use impacts on shallow groundwater temperatures. Average SGW temperature during the study period was 11.1 and 11.2 °C at the Ag and BHF sites, respectively. However, temperature range at the Ag site was 72% greater than at the BHF site. Results indicate a greater responsiveness to seasonal climate fluctuations in Ag site SGW temperature related to absence of forest canopy. Patterns of intra‐site groundwater temperature differences at both study sites illustrate the influence of stream–aquifer thermal conduction and occasional baseflow reversals. Considering similar surface soil temperature amplitudes and low average groundwater flow values at both sites, results suggest that contrasting rates of plant water use, groundwater recharge, and subsurface hydraulic conductivity are likely mechanistic causes for the observed SGW temperature differences. Results highlight the long‐term impact of forest removal on subsurface hydrology and groundwater temperature regime. Copyright © 2015 John Wiley & Sons, Ltd.     

Tidally-induced sediment transport patterns in the upper Bay of Fundy: A numerical study

The Minas Basin, the eastern end of the Bay of Fundy, is well known for its high tide ranges and strong tidal currents, which can be exploited to extract electricity power. The properties of the tidally-induced sediment transport in the Minas Basin, where significant changes in tidal processes may occur due to a recently proposed tidal power project, have been studied with a three-dimensional hydrodynamic model, an empirical bed load sediment transport model and surface sediment concentrations derived from the remotely-sensed images. The hydrodynamic model was evaluated against independent observational data, which include tidal elevation, tidal current (in the full water column and bottom layer), residual current profile and tidal asymmetry indicators. The evaluation shows that the model is in good agreement with the observations.The sediment transport includes two components, bed load and suspended particulate load. The bed load is calculated using the modelled bottom shear stress and the observed grain size data. The estimated features of bed load transport roughly agree with the observed patterns of the erosion and deposition in the Minas Basin and Cobequid Bay. The transport of the suspended load is estimated using the modelled velocity fields and the surface sediment concentration derived from remote-sensing images. The comparisons between the modelled results and the limited observations illustrate that the observed directions of suspended sediment transport are basically reproduced by the model. The modelled net suspended sediment input into the Minas Basin through Minas Passage is 2.4×10⁶ m³ yr^?1, which is comparable to the observed value of 1.6×10⁶ m³ yr^?1.The variations of the bed load and the suspended load in space and time are also presented. The total net transport, defined as the mean value of the sum of bed and suspended load transports during the tidal cycle, shows strong spatial variability. The magnitude of the transport flux ranges from 0.1 to 0.2 kg m^?1 s^?1 in Minas Channel and Minas Passage, 0.1 kg m^?1 s^?1 in Cobequid Bay, to 0.01 kg m^?1 s^?1 in the central Minas Basin and Southern Bight. In Minas Channel, the sediment transport follows the structure of the tidal residual circulation, which features a large anticlockwise gyre. The sediment in Minas Passage moves eastward and deposits into the central Minas Basin. However, the sediment from the eastern part of the Basin moves westward and deposits in the central Minas Basin as well. In the Cobequid Bay, sediment moves eastward and deposits in the upper bay.     

Nested‐Scale Nutrient Flux in a Mixed‐Land‐Use Urbanizing Watershed

To improve quantitative understanding of mixed‐land‐use impacts on nutrient yields, a nested‐scale experimental watershed study design (n = 5) was applied in a 303(d), clean water act impaired urbanizing watershed of the lower Missouri River Basin, USA. From 2010 to 2013, water samples (n = 858 sample days per site) were analysed for total inorganic nitrogen (TIN‐N), nitrite (NO₂–N) nitrate (NO₃–N), ammonia (NH₃–N), and total phosphorus (TP‐P). Annual, seasonal, and monthly flow‐weighted concentrations (FWCs) and nutrient yields were estimated. Mean nutrient concentrations were highest where agricultural land use comprised 58% of the drainage area (NH₃ = 0.111 mg/l; NO₂ = 0.045 mg/l; NO₃ = 0.684 mg/l, TIN = 0.840 mg/l; TP = 0.127 mg/l). Average TP‐P increased by 15% with 20% increased urban land use area. Highly variable annual precipitation was observed during the study with highest nutrient yields during 2010 (record setting wet year) and lowest nutrient yields during 2012 (extreme drought year). Annual TIN‐N and TP‐P yields exceeded 10.3 and 2.04 kg ha^?1 yr^?1 from the agricultural dominated headwaters. Mean annual NH₃–N, NO₂–N, NO₃–N, TIN‐N, and TP‐P yields were 0.742, 0.400, 4.24, 5.38, and 0.979 kg ha^?1 yr^?1, respectively near the watershed outlet. Precipitation accounted for the majority of the explained variance in nutrient yields (R² values from 0.68 to 0.85). Nutrient yields were also dependent on annual precipitation of the preceding year (R² values from 0.87 to 0.91) thus enforcing the great complexity of variable mixed‐land‐use mediated source‐sink nutrient yield relationships. Study results better inform land managers and best management practices designed to mitigate nutrient pollution issues in mixed‐land‐use freshwater ecosystems. Copyright © 2015 John Wiley & Sons, Ltd.     

Estimating stream solute loads from fixed frequency sampling regimes: the importance of considering multiple solutes and seasonal fluxes in the design of long‐term stream monitoring networks

Reduced sampling frequency is known to increase the error associated with estimates of stream solute load. However, the extent to which the magnitude of error differs among commonly measured solutes and across seasons is unclear. In this study, a high sampling frequency data set from two forested streams (one upland‐draining and one wetland‐draining stream) in south‐central Ontario was systematically sub‐sampled to simulate weekly, fortnightly and monthly fixed frequency sampling regimes for 12 stream solutes. We found that solutes which had a higher degree of temporal variation in concentration (i.e. higher %RSD) had poorer precision (C_v) in estimates of annual load relative to solutes with a lower %RSD. In addition, the magnitude and direction of bias varied considerably among solutes and were related to differences in spring concentration‐discharge relationships (m_{[spring Q vs C]}) among the 12 solutes. Solutes which decreased in concentration with increases in spring flow (i.e. m_{[spring Q vs C]} <0) exhibited positive bias in annual load while solutes which increased in concentration with increases in spring flow (i.e. m_{[spring Q vs C]} >0) were negatively biased. In terms of differences between seasonal and annual load errors, precision was generally lower for estimates of seasonal load relative to annual load while bias varied in both magnitude and direction among seasons. When the root mean square error (RMSE) of load estimates was compared to a threshold of acceptable error (<15%), the proportion of solutes attaining acceptable levels of uncertainty ranged from 11/12 for annual load estimates at a weekly sampling frequency to only 4/12 at a monthly frequency when both annual and seasonal loads were considered. Our results demonstrate that commonly measured solutes do not behave uniformly in response to changes in sampling frequency and that estimates of seasonal loads are often less accurate than estimates of annual load. These findings provide important insights into the design of stream monitoring programs and the evaluation of existing long‐term data sets. Copyright © 2015 John Wiley & Sons, Ltd.     

Use of soil‐streamwater relationships to assess regional patterns of acidic deposition effects in the northeastern USA

Declines of acidic deposition levels by as much as 50% since 1990 have led to partial recovery of surface waters in the northeastern USA but continued depletion of soil calcium through this same period suggests a disconnection between soil and surface water chemistry. To investigate the role of soil‐surface water interactions in recovery from acidification, the first regional survey to directly relate soil chemistry to stream chemistry during high flow was implemented in a 4144‐km² area of the Catskill region of New York, where acidic deposition levels are among the highest in the East. More than 40% of 95 streams sampled in the southern Catskill Mountains were determined to be acidified and had inorganic monomeric aluminum concentrations that exceeded a threshold that is toxic to aquatic biota. More than 80% likely exceeded this threshold during the highest flows, but less than 10% of more than 100 streams sampled were acidified in the northwestern portion of the region. Median Oa horizon soil base saturation ranged from 50% to 80% at 200 sites across the region, but median base saturation in the upper 10 cm of the B horizon was less than 20% across the region and was only 2% in the southern area. Aluminum is likely to be interfering with root uptake of calcium in the mineral horizon in approximately half the sampled watersheds. Stream chemistry was highly variable over the Catskill region and, therefore, did not always reflect the calcium depletion of the B horizon that our sampling suggested was nearly ubiquitous throughout the region. Published 2013. This article is a U.S. Government work and is in the public domain in the USA.     

Fluvial suspended sediment transfer and lacustrine sedimentation of recent flood turbidites in proglacial Eklutna Lake,western Chugach Mountains,Alaska

Suspended sediment delivery and deposition in proglacial lakes is generally sensitive to a wide range of hydrometeorologic and geomorphic controls. High discharge conditions are of particular importance in many glaciolacustrine records, with individual floods potentially recorded as distinctive turbidites. We used an extensive network of surface sediment cores and hydroclimatic monitoring data to analyse recent flood turbidites and associated sediment transfer controls over instrumental periods at Eklutna Lake, western Chugach Mountains, Alaska. Close to a decade of fluvial data from primary catchment tributaries show a dominating influence of discharge on sediment delivery, with various interconnections with other related hydroclimatic controls. Multivariate fluvial models highlight and help quantify some complexities in sediment transfer, including intra-annual variations, meteorological controls, and the influence of subcatchment glacierization. Sediments deposited in Eklutna Lake during the last half century are discontinuously varved and contain multiple distinctive turbidites. Over a 30-year period of stratigraphic calibration, we correlate the four thickest flood turbidites (1989, 1995, 2006, and 2012) to specific regional storms. The studied turbidites correlate with late-summer and early-autumn rainstorms with a magnitude of relatively instantaneous sedimentation 3–15 times greater than annual background accumulation. Our network of sediment core data captured the broad extent and sediment variability among the study turbidites and background sediment yield. Within-lake spatial modelling of deposition quantifies variable rates of downlake thinning and sediment focusing effects, and highlights especially large differences between the thickest flood turbidites and background sedimentation. This we primarily relate to strongly contrasting dispersion processes controlled by inflow current strength and turbidity. Sediment delivery is of interest for this catchment because of reservoir and water supply operations. Furthermore, although smaller floods may not be consistently represented, the lake likely contains a valuable proxy record of regional flooding proximal to major population centers of south-central Alaska including Anchorage.