A new method for the quantification of different redox-species of molybdenum (V and VI) in seawater

A new method for the direct determination of reduced and oxidized Mo species (Mo (V) and Mo (VI)) in seawater was developed and used for the first time. The method includes the complexation of Mo (V) with tartrate, solid phase extraction of the Mo (V)–tartrate complex by a XAD 7HP resin, followed by elution with acidic acetone. In this study, the eluted Mo (V) was quantified by graphite furnace atomic absorption spectrometry. The detection limit of this protocol was on the order of 0.2 nM. The analytical precision was 10% of ~ 10 nM. This method was successfully applied to the determination of Mo (V) and Mo (VI) in surface and bottom waters at the head of Peconic River Estuary. Total Mo (Mo (V) + Mo (VI)) ranged from 100–120 nM in most bottom saline waters, and 2.5–15 nM for surface fresher waters. Concentrations of Mo (V) in these environments ranged from 0 nM to ~ 15 nM, accounting for 0%–15% of the total dissolved Mo pool. The time series experiments showed that the Mo speciation changed within 1 h after the water collection, and therefore it is strongly suggested that speciation analysis be carried out within the first 15 min. However, since these are the first Mo speciation data in concentration ranges typical of normal marine and coastal waters, additional research may be required to optimize the methodology and further explore Mo cycling mechanisms.     

Morphology of the Itapeva to Tramandai transgressive dunefield barrier system and mid‐ to late Holocene sea level change

The surface morphology of the transgressive dunefield barrier extending from Itapeva to Tramandai along the northern littoral of Rio Grande do Sul, is examined and an attempt is presented to link morphological changes across the barrier to Holocene sea level changes. The 4·5 km wide Holocene barrier displays two typical morphologies: an inner part dominated by large‐scale, continuous alongshore, overlapping dunefield phases comprising sand sheets, dunes, deflation plains and precipitation ridges; and an outer part dominated by discontinuous, medium‐ to small‐scale, triangular to lobate transgressive dunefield phases, cut by both active and relict (palaeo‐) creeks or washouts. Holocene sea level in the region rose to c. +1 to +3 m above present reaching a maximum around 5100 years bp and then progressively fell to the present level. We argue that the effect on barrier development was to suppress the development of a drainage system during the rising and maximum stages, and encourage the development of an organized drainage system in the form of regularly spaced washouts during the falling period, and that this change in sea level from rising to falling therefore produced the large‐scale differences in barrier morphology. Copyright © 2006 John Wiley & Sons, Ltd.     

Enhanced data and methods for improving open and free global population grids: putting ‘leaving no one behind’ into practice

ABSTRACT

Data on global population distribution are a strategic resource currently in high demand in an age of new Development Agendas that call for universal inclusiveness of people. However, quality, detail, and age of census data varies significantly by country and suffers from shortcomings that propagate to derived population grids and their applications. In this work, the improved capabilities of recent remote sensing-derived global settlement data to detect and mitigate major discrepancies with census data is explored. Open layers mapping built-up presence were used to revise census units deemed as ‘unpopulated’ and to harmonize population distribution along coastlines. Automated procedures to detect and mitigate these anomalies, while minimizing changes to census geometry, preserving the regional distribution of population, and the overall counts were developed, tested, and applied. The two procedures employed for the detection of deficiencies in global census data obtained high rates of true positives, after verification and validation. Results also show that the targeted anomalies were significantly mitigated and are encouraging for further uses of free and open geospatial data derived from remote sensing in complementing and improving conventional sources of fundamental population statistics.     

The effect of chlorite interlayering on <Superscript>40</Superscript>Ar–<Superscript>39</Superscript>Ar biotite dating: an <Superscript>40</Superscript>Ar–<Superscript>39</Superscript>Ar laser-probe and TEM investigations of variably chloritised biotites

Biotite is one of the most common minerals dated by the ⁴⁰Ar–³⁹Ar method. It frequently shows K contents below the expected stoichiometric value, suggesting the presence of low-K impurities. The most common low-K alteration product of biotite is chlorite. Therefore, it is important to understand the effects of chlorite interlayering on ⁴⁰Ar–³⁹Ar ages in order to correctly interpret ⁴⁰Ar–³⁹Ar data. This study examines the outcome of ⁴⁰Ar–³⁹Ar dating analyses on variably chloritised biotites from Ordovician intrusive rocks. The infrared (IR) laser-probe technique and different gas extraction methods were adopted. Incremental laser-heating data on bulk samples yielded hump-shaped age profiles with meaningless young and old age steps. Both the extent of anomalous old age steps and the degree of discordance of the age spectra were much more pronounced in the more chloritised biotite samples. In contrast, in situ data on rock chips and total-fusion ages on single biotite flakes yielded ages concordant with, or younger than, the inferred emplacement ages. Transmission electron microscopy (TEM) was used to texturally characterise biotite samples at the nanometre scale. It was also used to document the complex decomposition-transformation process affecting interlayered biotite–chlorite during in-vacuo IR-laser heating to temperatures ranging from ~600 to >1,000 °C. TEM results suggest that hump-shaped age profiles result from an interplay between ³⁹Ar_K redistribution by recoil during sample irradiation and differential release of argon isotopes hosted in three main reservoirs. These reservoirs are (from least to most retentive): extended defects, chlorite and biotite. The final descending age segment is attributed to the progressive release of argon with increasing temperature from large biotite domains for which ³⁹Ar_K recoil loss was less important. ⁴⁰Ar–³⁹Ar data support previous findings, which suggest that ⁴⁰Ar–³⁹Ar ages when recoil effects are minimised, provide minimum estimates that approach the true biotite age, when the pristine domains are analysed. The most effective approach for obtaining meaningful ⁴⁰Ar–³⁹Ar ages was using individual total-fusion analyses on carefully selected, single flakes previously split along the basal cleavage by wet-grinding and corresponding to a sample mass of a few micrograms.Editorial responsibility: I Parsons     

Groundwater resource degradation in coastal plains: The example of the Cecina area (Tuscany – Central Italy)

The paper describes the degradation of the groundwater resources in the Cecina area, where seawater intrusion, B contamination and NO₃ pollution are all affecting the heavily exploited Pleistocene aquifer. Over-pumping has brought water levels to about 0 m.a.s.l. as far as about 7 km from the shore line, thereby promoting the seawater intrusion. The intrusion, which is characterized by cation exchange phenomena and Ca–Cl type waters, enters the plain mostly through the shallower horizons. The saline front, which advanced from 0.5 to 1 km in 4 a, has by now reached the foot of the hills to the east of the town, where it is also affecting wells of the local aqueduct. Boron contamination, linked to past discharge of industrial waste transported downstream by the river, reached concentrations as high as 3.5 mg/L in the mid-1980s. Although a decreasing trend is now under way, B content is still close to 1 mg/L. The presence of high NO₃, which, together with the seawater intrusion, represents a major issue for groundwater management in the area, is linked to the widespread utilization of fertilizers. Nitrate concentration, which reaches a maximum of about 300 mg/L in the shallow aquifer horizons and then decreases rather regularly with depth, is strongly influenced by precipitation. However, irrigation also contributes significantly to transporting the NO₃ contamination to depth, as clearly shown by δ¹⁸O data. The severe decline in the quality of the groundwater resource in the Cecina area is further compounded by an overall decrease in water availability in the region of Tuscany, as evidenced by long-term monitoring of precipitation and fluvial discharge.     

Importance of geochemical transformations in determining submarine groundwater discharge-derived trace metal and nutrient fluxes

Seasonal (Spring and Summer 2002) concentrations of dissolved (<0.22 μm) trace metals (Ag, Al, Co, Cu, Mn, Ni, Pb), inorganic nutrients (NO₃, PO₄, Si), and DOC were determined in groundwater samples from 5 wells aligned along a 30 m shore-normal transect in West Neck Bay, Long Island, NY. Results show that significant, systematic changes in groundwater trace metal and nutrient composition occur along the flowpath from land to sea. While conservative mixing between West Neck Bay water and the groundwaters explains the behavior of Si and DOC, non-conservative inputs for Co and Ni were observed (concentration increases of 10- and 2-fold, respectively) and removal of PO₄ and NO₃ (decreases to about half) along the transport pathway. Groundwater-associated chemical fluxes from the aquifer to the embayment calculated for constituents not exhibiting conservative behavior can vary by orders of magnitude depending on sampling location and season (e.g. Co, 3.4 × 10²– 8.2 × 10³ μmol d⁻¹). Using measured values from different wells as being representative of the true groundwater endmember chemical composition also results in calculation of very different fluxes (e.g., Cu, 6.3 × 10³ μmol d⁻¹ (inland, freshwater well) vs. 2.1 × 10⁵ μmol d⁻¹(seaward well, S = 17 ppt)). This study suggests that seasonal variability and chemical changes occurring within the subterranean estuary must be taken into account when determining the groundwater flux of dissolved trace metals and nutrients to the coastal ocean.