Provenance analysis using Raman spectroscopy of carbonaceous material: A case study in the Southern Alps of New Zealand

Detrital provenance analyses in orogenic settings, in which sediments are collected at the outlet of a catchment, have become an important tool to estimate how erosion varies in space and time. Here we present how Raman Spectroscopy on Carbonaceous Material (RSCM) can be used for provenance analysis. RSCM provides an estimate of the peak temperature (RSCM-T) experienced during metamorphism. We show that we can infer modern erosion patterns in a catchment by combining new measurements on detrital sands with previously acquired bedrock data. We focus on the Whataroa catchment in the Southern Alps of New Zealand and exploit the metamorphic gradient that runs parallel to the main drainage direction. To account for potential sampling biases, we also quantify abrasion properties using flume experiments and measure the total organic carbon content in the bedrock that produced the collected sands. Finally, we integrate these parameters into a mass-conservative model. Our results first demonstrate that RSCM-T can be used for detrital studies. Second, we find that spatial variations in tracer concentration and erosion have a first-order control on the RSCM-T distributions, even though our flume experiments reveal that weak lithologies produce substantially more fine particles than do more durable lithologies. This result implies that sand specimens are good proxies for mapping spatial variations in erosion when the bedrock concentration of the target mineral is quantified. The modeling suggests that highest present-day erosion rates (in Whataroa catchment) are not situated at the range front but around 10 km into the mountain belt.

The supergene thorium and rare-earth element deposit at Morro do Ferro, Poços de Caldas, Minas Gerais, Brazil

The thorium and rare-earth element (Th-REE) deposit at Morro do Ferro formed under supergene lateritic weathering conditions. The ore body consists of shallow NW-SE elongated argillaceous lenses that extend from the top of the hill downwards along its south-eastern slope. The deposit is capped by a network of magnetite layers which protected the underlying highly weathered, argillaceous host rock from excessive erosion. The surrounding country rocks comprise a sequence of subvolcanic phonolite intrusions that have been strongly altered by hydrothermal and supergene processes. From petrological, mineralogical and geochemical studies, and mass balance calculations, it is inferred that the highly weathered host rock was originally carbonatitic in composition, initially enriched in Th and REEs compared to the surrounding silicate rocks. The intrusion of the carbonatite caused fenitic alteration in the surrounding phonolites, consisting of early potassic alteration followed by a vein-type Th-REE mineralization with associated fluorite, carbonate, pyrite and zircon. Subsequent weathering has completely decomposed the carbonatite forming a residual supergene enrichment of Th and REEs. Initial weathering of the carbonatite has created a chemical environment that might have been conductive to carbonate and phosphate complexing of the REEs in groundwaters. This may have appreciably restricted the dissolution of primary REE phases. Strongly oxidic weathering has resulted in a fractionation between Ce and the other light rare earth elements (LREEs). Ce3+ is oxidized to Ce4+ and retained together with Th by secondary mineral formation (cerianite, thorianite), and by adsorption on poorly crystalline iron- and aluminium-hydroxides. In contrast, the trivalent LREEs are retained to a lesser degree and are thus more available for secondary mineral formation (Nd-lanthanite) and adsorption at greater depths down the weathering column. Seasonally controlled fluctuations of recharge waters into the weathering column may help to explain the observed repetition of Th-Ce enriched zones underlain by trivalent LREE enriched zones.

Fate and effects of drilling wastes in a shallow estuarine mesocosm

To address concerns expressed about the possible effect of drilling mud discharges on shallow, low-energy estuarine ecosystems, a 12 month study was designed to detect alterations in water quality and sediment geochemistry. Each drilling mud used in the study and sediments from the study site were analyzed in the laboratory for chemical and physical characteristics. Potential water quality impacts were simulated by the EPA-COE elutriation test procedure. Mud toxicity was measured by acute and chronic bioassays with Mysidopsis bahia, Mercenaria mercenaria, and Nereis virens.^ For the field study, a relatively pristine, shallow (1.2 m) estuary (Christmas Bay, TX) without any drilling activity for the last 30 years was chosen for the study site. After a three month baseline study, three stations were selected. Station 1 was an external control. At each treatment station (2, 3), mesocosms were constructed to enclose a 3.5 m$\sp3$ water column. Each treatment station included an internal control site also. Each in situ mesocosm, except the controls, was successively dosed at a mesocosm-specific dose (1:100; 1:1,000; or 1:10,000 v/v) with 4 field collected drilling muds (spud, nondispersed, lightly-treated, and heavily-treated lignosulfonate) in sequential order over 1.5 months. Twenty-four hours after each dose, water exchange was allowed until the next treatment. Station 3 was destroyed by a winter storm. After the last treatment, the enclosures were removed and the remaining sites monitored for 6 months. One additional site was similarly dosed (1:100 v/v) with clean dredged sediment from Christmas Bay for comparison between dredged sediments and drilling muds.^ Results of the analysis of the water samples and field measurements showed that water quality was impacted during the discharges, primarily at the highest dose (1:100 v/v), but that elevated levels of C, Cr (T,F), Cr$\sp{+3}$ (T, F), N, Pb, and Zn returned to ambient levels before the end of the 24 hour exposure period or immediately after water exchange was allowed (Al, Ba(T), Chlorophyll ABC, SS, %T). Barium, from the barite, was used as a geochemical tracer in the sediments to confirm estimated doses by mass balance calculations. Barium reached a maximum of 166x background levels at the high dose mesocosm. Barium levels returned to ambient or only slightly elevated levels at the end of the 6 month monitoring period due to sediment deposition, resuspension, and bioturbation. QA/QC results using blind samples consisting of lab standards and spiked samples for both water and sediment matrices were within acceptable coefficients of variation.^ In order to avoid impacts on water quality and sediment geochemistry in a shallow estuarine ecosystem, this study concluded that a minimal dilution of 1:1,000 (v/v) would be required in addition to existing regulatory constraints. ^

Strontium isotope ratios of pore waters and planktonic foraminifera from DSDP holes

A detailed record of the strontium-87 to strontium-86 ratio in seawater during the last 100 million years was determined by measuring this ratio in 137 well-preserved and well-dated fossil foraminifera samples. Sample preservation was evaluated from scanning electron microscopy studies, measured strontium-calcium ratios, and pore water strontium isotope ratios. The evolution of the strontium isotopic ratio in seawater offers a means to evaluate long-term changes in the global strontium isotope mass balance. Results show that the marine strontium isotope composition can be used for correlating and dating well-preserved authigenic marine sediments throughout much of the Cenozoic to a precision of +/- 1 million years. The strontium-87 to strontium-86 ratio in seawater increased sharply across the Cretaceous/Tertiary boundary, but this feature is not readily explained as strontium input from a bolide impact on land.

Ice and snow measurements during Nathaniel B. Palmer cruise NBP0709 (SIMBA experiment)

The Sea Ice Mass Balance in the Antarctic (SIMBA) experiment was conducted from the RVIB N.B. Palmer in September and October 2007 in the Bellingshausen Sea in an area recently experiencing considerable changes in both climate and sea ice cover. Snow and ice properties were observed at 3 short-term stations and a 27-day drift station (Ice Station Belgica, ISB) during the winter-spring transition. Repeat measurements were performed on sea ice and snow cover at 5 ISB sites, each having different physical characteristics, with mean ice (snow) thicknesses varying from 0.6 m (0.1 m) to 2.3 m (0.7 m). Ice cores retrieved every five days from 2 sites and measured for physical, biological, and chemical properties. Three ice mass-balance buoys (IMBs) provided continuous records of snow and ice thickness and temperature. Meteorological conditions changed from warm fronts with high winds and precipitation followed by cold and calm periods through four cycles during ISB. The snow cover regulated temperature flux and controlled the physical regime in which sea ice morphology changed. Level thin ice areas had little snow accumulation and experienced greater thermal fluctuations resulting in brine salinity and volume changes, and winter maximum thermodynamic growth of ~0.6 m in this region. Flooding and snow-ice formation occurred during cold spells in ice and snow of intermediate thickness. In contrast, little snow-ice formed in flooded areas with thicker ice and snow cover, instead nearly isothermal, highly permeable ice persisted. In spring, short-lived cold air episodes did not effectively penetrate the sea ice nor overcome the effect of ocean heat flux, thus favoring net ice thinning from bottom melt over ice thickening from snow-ice growth, in all cases. These warm ice conditions were consistent with regional remote sensing observations of earlier ice breakup and a shorter sea ice season, more recently observed in the Bellingshausen Sea.

The Austrian Glacier Inventories GI 1 (1969), GI 2 (1998), GI 3 (2006), and GI LIA in ArcGIS (shapefile) format

Glacier inventories provide the basis for further studies on mass balance and volume change, relevant for local hydrological issues as well as for global calculation of sea level rise. In this study, a new Austrian glacier inventory has been compiled, updating data from 1969 (GI 1) and 1998 (GI 2) based on high-resolution lidar digital elevation models (DEMs) and orthophotos dating from 2004 to 2012 (GI 3). To expand the time series of digital glacier inventories in the past, the glacier outlines of the Little Ice Age maximum state (LIA) have been digitalized based on the lidar DEM and orthophotos. The resulting glacier area for GI 3 of 415.11 ± 11.18 km**2 is 44% of the LIA area. The annual relative area losses are 0.3%/yr for the ~119-year period GI LIA to GI 1 with one period with major glacier advances in the 1920s. From GI 1 to GI 2 (29 years, one advance period of variable length in the 1980s) glacier area decreased by 0.6% yr?1 and from GI 2 to GI 3 (10 years, no advance period) by 1.2%/yr. Regional variability of the annual relative area loss is highest in the latest period, ranging from 0.3 to 6.19%/yr. The mean glacier size decreased from 0.69 km**2 (GI 1) to 0.46 km**2 (GI 3), with 47% of the glaciers being smaller than 0.1 km**2 in GI 3 (22%).

Daily polynya area and ice production in the North Water polynya region

The North Water (NOW) Polynya is a regularly-forming area of open-water and thin-ice, located between northwestern Greenland and Ellesmere Island (Canada) at the northern tip of Baffin Bay. Due to its large spatial extent, it is of high importance for a variety of physical and biological processes, especially in wintertime. Here, we present a long-term remote sensing study for the winter seasons 1978/1979 to 2014/2015. Polynya characteristics are inferred from (1) sea ice concentrations and brightness temperatures from passive microwave satellite sensors (Advanced Microwave Scanning Radiometer (AMSR-E and AMSR2), Scanning Multichannel Microwave Radiometer (SMMR), Special Sensor Microwave Imager/Sounder (SSM/I-SSMIS)) and (2) thin-ice thickness distributions, which are calculated using MODIS ice-surface temperatures and European Center for Medium-Range Weather Forecasts (ECMWF) atmospheric reanalysis data in a 1D thermodynamic energy-balance model. Daily ice production rates are retrieved for each winter season from 2002/2003 to 2014/2015, assuming that all heat loss at the ice surface is balanced by ice growth. Two different cloud-cover correction schemes are applied on daily polynya area and ice production values to account for cloud gaps in the MODIS composites. Our results indicate that the NOW polynya experienced significant seasonal changes over the last three decades considering the overall frequency of polynya occurrences, as well as their spatial extent. In the 1980s, there were prolonged periods of a more or less closed ice cover in northern Baffin Bay in winter. This changed towards an average opening on more than 85% of the days between November and March during the last decade. Noticeably, the sea ice cover in the NOW polynya region shows signs of a later-appearing fall freeze-up, starting in the late 1990s. Different methods to obtain daily polynya area using passive microwave AMSR-E/AMSR2 data and SSM/I-SSMIS data were applied. A comparison with MODIS data (thin-ice thickness < 20 cm) shows that the wintertime polynya area estimates derived by MODIS are about 30 to 40% higher than those derived using the polynya signature simulation method (PSSM) with AMSR-E data. In turn, the difference in polynya area between PSSM and a sea ice concentration (SIC) threshold of 70% is fairly low (approximately 10%) when applied to AMSR-E data. For the coarse-resolution SSM/I-SSMIS data, this difference is much larger, particularly in November and December. Instead of a sea ice concentration threshold, the PSSM method should be used for SSM/I-SSMIS data. Depending on the type of cloud-cover correction, the calculated ice production based on MODIS data reaches an average value of 264.4 ± 65.1 km**3 to 275.7 ± 67.4 km**3 (2002/2003 to 2014/2015) and shows a high interannual variability. Our achieved long-term results underline the major importance of the NOW polynya considering its influence on Arctic ice production and associated atmosphere/ocean processes.