Recent distribution of lead in the Indian Ocean reflects the impact of regional emissions.

Humans have injected lead (Pb) massively into the earth surface environment in a temporally and spatially evolving pattern. A significant fraction is transported by the atmosphere into the surface ocean where we can observe its transport by ocean currents and sinking particles. This study of the Indian Ocean documents high Pb concentrations in the northern and tropical surface waters and extremely low Pb levels in the deep water. North of 20°S, dissolved Pb concentrations decrease from 42 to 82 pmol/kg in surface waters to 1.5-3.3 pmol/kg in deep waters. South of 20°S, surface water Pb concentrations decrease from 21 pmol/kg at 31°S to 7 pmol/kg at 62°S. This surface Pb concentration gradient reflects a southward decrease in anthropogenic Pb emissions. The upper waters of the north and central Indian Ocean have high Pb concentrations resulting from recent regional rapid industrialization and a late phase-out of leaded gasoline, and these concentrations are now higher than currently seen in the central North Pacific and North Atlantic oceans. The Antarctic sector of the Indian Ocean shows very low concentrations due to limited regional anthropogenic Pb emissions, high scavenging rates, and rapid vertical mixing, but Pb still occurs at higher levels than would have existed centuries ago. Penetration of Pb into the northern and central Indian Ocean thermocline waters is minimized by limited ventilation. Pb concentrations in the deep Indian Ocean are comparable to the other oceans at the same latitude, and deep waters of the central Indian Ocean match the lowest observed oceanic Pb concentrations.

Determination of ultra-trace Te species in open ocean waters based on Mg(OH)2 coprecipitation, anion exchange resin column separation and inductively coupled plasma sector-field mass spectrometry using a 125Te-enriched isotope spike.

We present a method for the determination of ultra-trace Te species (Te(IV) and Te(VI)) in open ocean waters. The proposed method is based on Mg(OH)2 coprecipitation, anion exchange resin column separation and inductively coupled plasma sector-field mass spectrometry (ICPSFMS) using a 125Te-enriched isotope spike. The largest advantage of the method is that the use of the spike allows accurate and precise determination when it combines with either isotope dilution or recovery correction. Tellurium-IV and VI are preconcentrated in a Mg(OH)2 precipitate and separated mutually by an anion exchange resin column. Te(IV) is retained to the column, while Te(VI) passing through the column is recovered by a subsequent column procedure after reduction of Te(VI) to Te(IV). Te(IV) is successfully eluted with a small amount of 0.01 M HCl. The additional merit of using this eluent is elimination of components that result in a memory effect during the measurement of Te(IV). Possible mass spectral interference on Te(IV) can be excluded by adjusting the mass window, and the Te(IV) concentrations determined by this approach agree well with those independently obtained by an oxidation procedure which removes the interference. The accuracy of the proposed method is verified with homemade standard seawater for which the measured concentrations agree well with results calculated from the value of the standard solution. Procedural blanks for Te(IV) and Te(VI) are 1.5 ± 0.9 pg kg-1 (n = 11) and 1.3 ± 0.9 pg kg-1 (n = 11) with corresponding overall detection limits of 3.0 pg kg-1 and 2.8 pg kg-1, respectively. Using the method, we have clarified vertical profiles of Te(IV) and Te(VI) in the subarctic western North Pacific for the first time.

Iron-catalyzed aromatic amination for nonsymmetrical triarylamine synthesis.

Novel iron-catalyzed amination reactions of various aryl bromides have been developed for the synthesis of diaryl- and triarylamines. The key to the success of this protocol is the use of in situ generated magnesium amides in the presence of a lithium halide, which dramatically increases the product yield. The present method is simple and free of precious and expensive metals and ligands, thus providing a facile route to triarylamines, a recurrent core unit in organic electronic materials as well as pharmaceuticals.

Multielemental determination of GEOTRACES key trace metals in seawater by ICPMS after preconcentration using an ethylenediaminetriacetic acid chelating resin.

GEOTRACES is an international research project on marine biogeochemical cycles of trace elements and their isotopes. GEOTRACES key trace metals in seawater are Al (8-1000 ng/kg), Mn (4-300 ng/kg), Fe (1-100 ng/kg), Cu (30-300 ng/kg), Zn (3-600 ng/kg), and Cd (0.1-100 ng/kg), of which global oceanic distribution will be determined on a number of research cruises. This work introduces a novel method of solid-phase extraction to determine Al, Mn, Fe, Co, Ni, Cu, Zn, Cd, and Pb in seawater by adjusting the pH of the sample to 6 and carrying out a single preconcentration step. The trace metals were collected from approximately 120 mL of seawater using a column of a chelating resin containing the ethylenediaminetriacetic acid functional group and eluted with approximately 15 mL of 1 M HNO3. Mn and Fe in the eluate were measured by inductively coupled plasma mass spectrometry (ICPMS) using the dynamic reaction cell mode, and the other metals were measured using the standard mode. Using this procedure, the trace metals were collected quantitatively, while >99.9% of alkali and alkaline earth metals in seawater were removed. The procedural blank was <7% of the mean concentration in deep ocean waters, except 16% for Pb. The overall detection limit was <14% of the mean concentration in deep ocean waters. The RSD was <9%. Our values for the trace metals in the certified reference materials of seawater NASS-5 and nearshore seawater CASS-4 agreed with the certified values (except that there is no certified value for Al). This method was also successfully applied to the reference materials of open-ocean seawater produced by the SAFe program. Our Fe concentrations were 5.9 +/- 0.7 ng/kg for surface water (S1) and 50.4 +/- 2.9 ng/kg for deep water (D2), which are in agreement with the interlaboratory averages of 5.4 +/- 2.4 and 50.8 +/- 9.5 ng/L, respectively. The data for other metals were oceanographically consistent.

Determination of bismuth in open ocean waters by inductively coupled plasma sector-field mass spectrometry after chelating resin column preconcentration.

A novel low-blank method is described for the analysis of bismuth in seawater based on preconcentration using an ethylenediaminetriacetic acid chelating resin column followed by determination with inductively coupled plasma sector-field mass spectrometry (ICPSFMS). A sample is siphoned into and drains through the column with the flow rate being kept constant by using a flotation device. Bi in 250 mL of acidified seawater is extracted onto the column in this process and eluted with 2 mL of 3 M HNO(3) followed by 3 mL of ultra-high purity water. The concentration of Bi in the eluate is measured by ICPMS. The benefits of the method compared to others are its simplicity, a smaller amount of seawater, and lower procedural blanks and detection limits at pg kg(-1) levels. Data on dissolved Bi in open ocean reference samples of SAFe and GEOTRACES programs are presented for the first time.

Precise isotopic analysis of Mo in seawater using multiple collector-inductively coupled mass spectrometry coupled with a chelating resin column preconcentration method.

It is widely recognized that the natural isotopic variation of Mo can provide crucial information about the geochemical circulation of Mo, and the ocean is an important reservoir of Mo. To obtain precise isotopic data on Mo in seawater samples using multiple collector-inductively coupled plasma mass spectrometry (MC-ICPMS), we have developed a preconcentration technique using 8-hydroxyquinoline bonded covalently to a vinyl polymer resin (TSK-8HQ). By optimizing the procedure, Mo in seawater could be effectively separated from matrix elements such as alkali, alkaline earth, and transition metals. With this technique, even with a 50-fold enrichment factor, the changes in the 98Mo/95Mo ratio during preconcentration were smaller than twice the standard deviation (SD) in this study. Mass discrimination of Mo isotopes during the measurement was externally corrected for by normalizing 86Sr/88Sr to 0.1194 using an exponential law. We evaluated delta98/95Mo to a precision of +/- 0.08 per thousand (+/-2 SD); this value was found to be less than one-third of previous reported values. Moreover, we were able to determine an accurate ratio for every pair of stable Mo isotopes, which was impossible with previous methods owing to the isobaric interference from the external elements (Zr and Ru). In this study, delta92/98Mo in seawater was first determined so that it had the smallest relative error. We applied the proposed method to four kinds of seawater samples. The Mo compositions were constant among them, with average delta98/95Mo and delta92/98Mo values of 2.45 +/- 0.11 and -4.94 +/- 0.09 per thousand (+/-2 SD), respectively. Our data indicate that seawater is enriched in heavy Mo isotopes than previously reported.

Simultaneous determination of suspended particulate trace metals (Co, Ni, Cu, Zn, Cd and Pb) in seawater with small volume filtration assisted by microwave digestion and flow injection inductively coupled plasma mass spectrometer.

A new technique for the determination of suspended particulate trace metals (P-metals >0.2 microm), such as Co, Ni, Cu, Zn, Cd and Pb, in open ocean seawater has been developed by using microwave digestion coupled with flow injection inductively coupled plasma mass spectrometry (FI-ICP-MS). Suspended particulate matter (SPM) was collected from 500 mL of seawater on a Nuclepore filter (0.2 microm) using a closed filtration system. Both the SPM and filter were completely dissolved by microwave digestion. Reagents for the digestion were evaporated using a clean evaporation system, and the metals were redissolved in 0.8 M HNO3. The solution was diluted with buffer solution to give pH 5.0 and the metals were determined by FI-ICP-MS using a chelating adsorbent of 8-hydroxyquinoline immobilized on fluorinated metal alkoxide glass (MAF-8HQ). The procedure blanks with a filter were found to be 0.048+/-0.008, 10.3+/-0.3, 0.27+/-0.05, 3.3+/-1.8, 0.02+/-0.03 and 0.85+/-0.09 ng L(-1) for Co, Ni, Cu, Zn, Cd and Pb, respectively (n=14). Detection limits defined as 3 times the standard deviation of the blanks were 0.023, 0.90, 0.14, 5.3, 0.078 and 0.28 ng L(-1) for Co, Ni, Cu, Zn, Cd and Pb, respectively. Accuracy was evaluated using certified reference materials of chlorella (NES CRM No. 3) and marine sediment (HISS-1). The method was applied to the determination of vertical distributions for P-Co, Ni, Cu, Zn, Cd and Pb in the Western North Pacific.

Preconcentration of Zr, Hf, Nb, Ta and W in seawater using solid-phase extraction on TSK-8-hydroxyquinoline resin and determination by inductively coupled plasma-mass spectrometry.

Here, we present the first simultaneous preconcentration and determination of ultratrace (pmol kg(-1) level) Zr, Hf, Nb, Ta and W in seawater, both in the form of dissolved and acid-dissolvable species. 8-Hydroxyquinoline (8HQ) bonded covalently to a vinyl polymer resin, TSK-8HQ, was used in a chelating adsorbent column to concentrate the metals. The greatest advantage of this resin is its endurance to 5M HF, since this is an effective eluent for all five metals. The analytes were successfully concentrated from 250 mL seawater with a 50-fold concentration factor through the column extraction and evaporation. The detection limit was 0.009-0.15 pmol kg(-1). The procedure blank determined using ultra pure water as a sample was 0.005-0.37 pmol kg(-1). The five metals were quantitatively recovered from seawater with good precision (2-4%). The effect of sample pH, sample flow rate, eluent composition and sample pretreatment were carefully studied. This method was applied to seawater.