No abstract

Contaminants in sediments are less available than their concentrations might imply, but measures of this availability have been generally lacking. Sediments ingested by benthic animals can be expected to undergo a unique chemical environment controlled by the digestive chemistry of the organism. We measured solubilization of sedimentary contaminantsCu, Pb, and polycyclic aromatic hydrocarbons (PAH)by digestive fluids extracted from marine invertebrates. Bioavailability of these contaminants, thus measured, is a small fraction of total contaminant loadingtypically 1−10%. The amounts of metals solubilized by digestive fluids were orders of magnitude greater than would be predicted from water−solid partitioning with clean seawater, although they correlated well with solubilization by seawater. Digestive fluids from two different animal species solubilized different amounts of metals, indicating that bioavailability varies among species even under constant mode of uptake. High concentrations of solubilizing agents, such as amino acids for metals and surfactants for PAH, in the digestive fluids can explain the enhanced solubilization. This biomimetic approach to contaminant measurement provides the basis for more accurate mechanistic and routine assessments of environmental impact.

No abstract

No abstract

A long known way of anchoring isotope ratio values to the SI system is by means of gravimetrically prepared isotopic mixtures. Thermal ionization mass spectrometry (TIMS) is the traditionally associated measurement technique, but multi-collector double focusing inductively coupled plasma (MC-ICP)-MS now appears to be an attractive alternative. This absolute calibration strategy necessitates that mass discrimination effects remain invariant in time and across the range of isotope ratios measured. It is not the case with MC-ICPMS and the present work illustrates, in the case of Zn isotopic measurements carried out using locally produced synthetic Zn isotope mixtures (IRMM-007 series), how this calibration strategy must be adjusted. First, variation in mass discrimination effects across the measurement sequence is propagated as an uncertainty component. Second, linear proportionality during each individual measurement between normalized mass discrimination and the average mass of the isotope ratios is used to evaluate mass discrimination for the ratios involving low abundance isotopes. Third, linear proportionality between mass discrimination and the logarithm of the isotope ratio values for n(67Zn)/n(64Zn) and n(68Zn)/n(64Zn) in the mixtures is used iteratively to evaluate mass discrimination for the same ratios in the isotopically enriched materials. Fourth, ratios in natural-like materials (including IRMM-3702 and IRMM-651) are calibrated by external bracketing using the isotopic mixtures. The relative expanded uncertainty (k = 2) estimated for n(68Zn)/n(64Zn) and n(67Zn)/n(64Zn) ratio values in the synthetic isotopic mixtures and the natural-like zinc samples was in the range of 0.034 to 0.048%. The uncertainty on the weighing (0.01%, k = 1) was the largest contributor to these budgets. The agreement between these results and those obtained with a single detector TIMS and with another MC-ICPMS further validated this work. The absolute isotope ratio values found for IRMM-3702-material also proposed as "delta 0" for delta-scale isotopic measurements-are n(66Zn)/n(64Zn) = 0.56397 (30), n(67Zn)/n(64Zn) = 0.082166 (35), n(68Zn)/n(64Zn) = 0.37519 (16), and n(70Zn)/n(64Zn) = 0.012418 (23). The derived Zn atomic weight value Ar(Zn) = 65.37777 (22) differs significantly from the current IUPAC value by Chang et al. [1]. Remeasurement, with isotopic mixtures from the IRMM-007 series, of the Zn isotope ratios in the same Chang et al. [1] material have revealed large systematic differences (1.35 (27)% per atomic mass unit) that suggest unrecognized measurement biases in their results.

A sensitive method for the determination of ultratrace organotin species in seawater is described. The merits and demerits of derivatization methods using Grignard reagent or sodium tetraethylborate (NaBEt4) were evaluated in terms of derivatization efficiency, applicability to the programmed temperature vaporization (PTV) method, and procedural blanks. The sensitivity of the gas chromatography/inductively coupled plasma mass spectrometry (GC/ICPMS) was improved by more than 100-fold by operating the shield torch at normal plasma conditions, compared with that obtained without using it. The absolute detection limit as tin reached subfemtogram (fg) levels. Furthermore, the detection limit in terms of relative concentration was improved 100-fold by using the PTV method, which enabled the injection of a large sample volume of as much as 100 microL without loss of analyte. When the organotin species in seawater were extracted into hexane with a preconcentration factor of 1000 after ethylation with NaBEt4 and a 100 microL aliquot of the extract was injected into the GC, the instrumental detection limit in relative concentration reached 0.01 pg/L in original seawater. Sources of contamination of organotin species during the sample preparation were examined, and a purification method of NaBEt4 was developed. Finally, the method was successfully applied to open ocean seawater samples containing organotin species at the level of 1-100 pg/L.

A sensitive method for multielemental speciation analysis of volatile metal and metalloid compounds in air has been developed. The analytes are sampled simultaneously in the field by cryofocusing on a small glass wool-packed column at -175 °C. Detection is performed in the laboratory by low-temperature GC hyphenated with ICPMS. Oxygen addition in the carrier gas was used to reduce interferences originating from the presence of volatile carbon-containing species in the samples. Plasma stability during analysis was monitored continuously by internal standardization (Xe). This system provides routine absolute detection limits of 0.06-0.07 pg (as Pb) for tetraalkyllead species (Me(4)Pb, Et(4)Pb), 0.2 pg (as Sn) for tetraalkyltin species (Me(4)Sn, Et(4)Sn), 0.8 pg (as Hg) for mercury species (Hg(0), Me(2)Hg, Et(2)Hg), and 2.5 pg (as Se) for selenium species (Me(2)Se). This instrumentation makes it possible to collect small air sample volumes and has been successfully applied to the determination of volatile metal and metalloid species in the atmosphere in urban and rural locations. Qualitative application in the semiconductor industry is also reported with regard to the detection of arsenic (ASH(3), tert-butylarsine), phosphorus (PH(3), tert-butylphosphine), alkylindium, and gallium species.

Sediment particles passing through the guts of deposit feeders are subject to an environment unusually rich in dissolved organic material, especially proteinaceous materials, capable of binding metals. Concentrations of many heavy metals are high in gut fluids of various deposit feeders from pristine environments. Concentrations of Cu and Cd show strong correlations with total acid-hydrolyzed amino acids (TAHAA) in gut fluids in a cross-phyletic survey of 35 deposit feeder species. Similar correspondence with TAHAA obtains among individuals, along longitudinal gut sections, and among molecular weight fractions. Multiple incubations of sediments with a commercial protein solution having similar TAHAA concentration as gut fluid solubilized many metals, showing convergence toward similar composition as gut fluid. Adherence of gut-dissolved metal concentrations to the Irving-Williams order suggests that the rich milieu of soft ligands contained in gut fluids provides a mechanism for mobilization of softer metals in sediments.Dense populations of marine deposit-feeding invertebrates often process large amounts of sediment. As an example, individuals of the lugworm (Arenicola marina, Polychaeta), a common nonselective deposit-feeder species in sandy intertidal zones (Flach and Beukema 1994), can ingest up to 20ϫ their body weight of wet sediments per day (Cadée 1976). Studies on the effects of bioturbation on geochemistry of metals in sediment often emphasize physical movement of particles caused by feeding and burrowing of this species (e.g., Rasmussen et al. 1998), while the impact of digestive processes occurring in the guts of these animals has been largely ignored.Functionally, the tubular guts of deposit feeders often resemble a plug-flow reactor (Penry and Jumars 1987) where transiting sediments are processed. These animals secrete a wide range of digestive agents (e.g., enzymes and surfac-1 Corresponding author (lmayer@maine.edu).