Rapa Nui (Easter Island) Rano Raraku crater lake basin: Geochemical characterization and implications for the Ahu-Moai Period.

Rano Raraku, the crater lake constrained by basaltic tuff that served as the primary quarry used to construct the moai statues on Rapa Nui (Easter Island), has experienced fluctuations in lake level over the past centuries. As one of the only freshwater sources on the island, understanding the present and past geochemical characteristics of the lake water is critical to understand if the lake could have been a viable freshwater source for Rapa Nui. At the time of sampling in September 2017, the maximum lake depth was ~1 m. The lake level has substantially declined in the subsequent years, with the lake drying almost completely in January 2018. The lake is currently characterized by highly anoxic conditions, with a predominance of ammonium ions on nitrates, a high concentration of organic carbon in the water-sediment interface and reducing conditions of the lake, as evidenced by Mn/Fe and Cr/V ratios. Our estimates of past salinity inferred from the chloride mass balance indicates that it was unlikely that Rano Raraku provided a viable freshwater source for early Rapa Nui people. The installation of an outlet pipe around 1950 that was active until the late 1970s, as well as grazing of horses on the lake margins appear to have significantly impacted the geochemical conditions of Rano Raraku sediments and lake water in recent decades. Such impacts are distinct from natural environmental changes and highlight the need to consider the sensitivity of the lake geochemistry to human activities.

Exploring the possibility to detect recent temporal changes in highly disturbed sedimentary records through sampling repetitions and core comparisons of porosity and sand content.

Dating of sediment cores in dynamic environments (such as tropical coastal lagoons) is often impossible to achieve, due to the difficulty to recover continuous and undisturbed records. Detailed temporal definition of environmental changes cannot be assured, but there is the possibility that information retained in such sediments can still provide useful insights on local or large-scale sedimentary dynamics, when a specific strategy is adopted. This latter consists in repeated core samplings at the same location and in the comparison of core profiles for basic and easily measurable parameters (porosity and sand content). This approach was tested on sediment cores, collected repeatedly during the period 2005-2010, at the same site of the Thi Nai Lagoon (central Vietnam). The proposed procedure was able to evidence the impact on lagoon sediments of activities linked to the construction of industrial settlements in the area, with dredging removing a consistent sediment layer from 2005 to 2008 and waste dumping providing additional sediment input in the following period. Simple statistic confirmed this scenario, together with core profiles of PCBs, As, Cd, Pb, and Zn. The procedure represents a simple tool to study coastal dynamics in places where the level of accuracy of traditional sediment radiodating cannot be reached. Several ameliorations are suggested in order to help developing the monitoring of sedimentary processes in poorly studied areas.

Determination of rare earth elements in tomato plants by inductively coupled plasma mass spectrometry techniques.

In recent years identification of the geographical origin of food has grown more important as consumers have become interested in knowing the provenance of the food that they purchase and eat. Certification schemes and labels have thus been developed to protect consumers and genuine producers from the improper use of popular brand names or renowned geographical origins. As the tomato is one of the major components of what is considered to be the healthy Mediterranean diet, it is important to be able to determine the geographical origin of tomatoes and tomato-based products such as tomato sauce. The aim of this work is to develop an analytical method to determine rare earth elements (RRE) for the control of the geographic origin of tomatoes. The content of REE in tomato plant samples collected from an agricultural area in Piacenza, Italy, was determined, using four different digestion procedures with and without HF. Microwave dissolution with HNO3 + H2O2 proved to be the most suitable digestion procedure. Inductively coupled plasma quadrupole mass spectrometry (ICPQMS) and inductively coupled plasma sector field plasma mass spectrometry (ICPSFMS) instruments, both coupled with a desolvation system, were used to determine the REE in tomato plants in two different laboratories. A matched calibration curve method was used for the quantification of the analytes. The detection limits (MDLs) of the method ranged from 0.03 ng g(-1) for Ho, Tm, and Lu to 2 ng g(-1) for La and Ce. The precision, in terms of relative standard deviation on six replicates, was good, with values ranging, on average, from 6.0% for LREE (light rare earth elements) to 16.5% for HREE (heavy rare earth elements). These detection limits allowed the determination of the very low concentrations of REE present in tomato berries. For the concentrations of REE in tomato plants, the following trend was observed: roots > leaves > stems > berries.

Speciation analysis of mercury in seawater from the lagoon of Venice by on-line pre-concentration HPLC-ICP-MS.

A method based on the coupling of HPLC with ICP-MS with an on-line pre-concentration micro-column has been developed for the analysis of inorganic and methyl mercury in the dissolved phase of natural waters. This method allows the rapid pre-concentration and matrix removal of interferences in complex matrices such as seawater with minimal sampling handling. Detection limits of 0.07 ng L(-1) for inorganic mercury and 0.02 ng L(-1) for methyl mercury have been achieved allowing the determination of inorganic mercury and methyl mercury in filtered seawater from the Venice lagoon. Good accuracy and reproducibility was demonstrated by the repeat analysis of the certified reference material BCR-579 coastal seawater. The developed HPLC separation was shown to be also suitable for the determination of methyl mercury in extracts of the particulate phase.

Complexation of cadmium and copper by fluvial humic matter and effects on their toxicity.

The effects of humic acids and fulvic acids isolated from the River Arno (Italy) on the bioavailability and toxicity of cadmium and copper were assessed in relation to changes in their speciation. Measurements of the complexing capacity of solutions containing these organic ligands were carried out by a titration procedure followed by DPASV and toxicity tests were carried out using lysosomes isolated from rat liver. The complexing capacity of the physiological medium containing about 13 mg/L of humic acids, expressed as ligand concentrations, was 0.30 and 0.072 micromol/L for cadmium and copper respectively; the corresponding conditional stability constants were 4.2 x 10(11) and 1.3 x 10(8) (mol/L)-1. The complexing capacities of the solution containing the same amount of fulvic acids were 0.33 and 0.164 micromol/L for cadmium and copper respectively, the conditional stability constants were 3.2 x 10(11) and 2.4 x 10(7) (mol/L)-1. The humic acids reduced the toxicity of cadmium by about 5 times: the EC50 changed from 4.4 to 20.4 micromol/L. The dose effect curve of copper presented a bi-sigmoid trend and two EC50 values can be determined: The EC50(1) in the presence of humic acids changed from 2.0 to 3.1 micromol/L, while the EC50(2) increased from 22.3 to 45.3 micromol/L. The fulvic acids reduced the cadmium toxicity by about the same amount as humic acids, from 4.4 to 18.6 micromol/L, but they had no effect on copper toxicity. Analysing the chemical speciation of cadmium and copper in the presence of humic components and under toxicity test conditions we can say that the appreciable decrease of EC50 is not related to changes in their speciation; we can hypothesize that this is due to different processes, as well as to blocking of the lysosomal membrane. On the basis of the shape of the dose-effect curves obtained for cadmium and copper respectively, we can say that the toxic effects of the two metals are different and we can hypothesize that copper could exercise its toxic activity by inhibiting the ATP-driven proton pump and the function of the Cl- selective channel.

Summer distribution of trace metals in the western sector of the Ross Sea, Antarctica.

The more important water masses generated by the interaction of Circumpolar Deep Water and the shelf waters in the western sector of the Ross Sea are characterized for trace element contents. The distribution of cadmium, lead, copper, zinc, iron, manganese and chromium during the austral summer is analysed and discussed according to the physical, chemical and biological processes which affect the composition of the water masses. The Cd concentration is found to have a relative high variability that can be related to biological activity and the water mass age, MCDW presents a mean dissolved concentration (SD) of 0.77 (0.07) nmol kg(-1), while the HSSW and AASW have a mean concentration of 0.63 (0.06) and 0.61 (0.16) nmol kg(-1), respectively. Lead features the typical distribution of a scavenged element with a surface maximum ranging between 22 and 130 pmol kg(-1) decreasing to 11 pmol kg(-1) in deep waters. However, the vertical distribution in the shelf area features a maximum concentration in intermediate/deep waters and we can hypothesize that the distribution may be influenced by more than one source. The surface dissolved concentration of zinc and copper were un-homogeneously distributed, the mean (SD) values were 5.25 (2.92) and 1.99 (1.49) nmol kg(-1) for zinc and copper, respectively and increased with depth for both the elements. We may therefore hypothesize enrichment in the dissolved phase deriving from recycling in deep waters. 95% of the chromium was in dissolved form and showed a superficial depletion; the mean concentrations were 1.6 +/- 0.2 and 2.6 +/- 0.8 nmol kg(-1) for surface and deep waters respectively. The vertical distribution of dissolved manganese was quite homogeneous with a mean concentration 0.96 +/- 0.7 nmol kg(-1). The particulate iron and manganese concentration trends are similar and feature a significant bottom increase implying a significant input from resuspension; the mean concentration of particulate ranged between 1.4 and 7.4 nmol kg(-1) for iron and ranged between 0.072 and 0.29 nmol kg(-1) for manganese.

Trace metals in aerosol at Terra Nova Bay, Antarctica.

Atmospheric particulate with an aerodynamic diameter <10 microm (PM10) was sampled continuously during the austral summers of 2000-2001 and 2001-2002 at a coastal site near to the Italian base of Terra Nova, Antarctica. Li, Pb, Cd, U, Ba, Bi, Cs, Rb, Tl, Sr, Al, V, Fe, Cu, Mn, Zn, Co, Ag were determined by inductively coupled sector field mass spectroscopy (ICP-SFMS) after sample digestion by a combination of HF, HNO3, and H2O2 in ultraclean conditions. Quality control of the analytical procedure was carried out by blank control, by evaluating the limits of detection, recoveries and repeatability. Concentrations found are extremely low for most metals, confirming the high purity of Antarctic aerosol. Principal Component Analysis (PCA) highlights high correlations among Pb, Cr, Bi, Cu and Zn concentration values and among Li, U, Ba, Cs, Rb, Al, V, Fe, Mn, Co concentration values permitting the identification of two principal source groups, namely crustal dust and human emission activities. Elements of anthropogenic origins (Pb, Cr, Cu, Zn) were highly enriched with respect to their crustal composition.