Because of increased interest in the marine and atmospheric sciences in elemental carbon (EC), or black carbon (BC) or soot carbon (SC), and because of the difficulties in analyzing or even defining this pervasive component of particulate carbon, it has become quite important to have appropriate reference materials for intercomparison and quality control. The NIST “urban dust” Standard Reference Material® SRM 1649a is useful in this respect, in part because it comprises a considerable array of inorganic and organic species, and because it exhibits a large degree of (14C) isotopic heterogeneity, with biomass carbon source contributions ranging from about 2 % (essentially fossil aliphatic fraction) to about 32 % (polar fraction).A primary purpose of this report is to provide documentation for the new isotopic and chemical particulate carbon data for the most recent (31 Jan. 2001) SRM 1649a Certificate of Analysis. Supporting this is a critical review of underlying international intercomparison data and methodologies, provided by 18 teams of analytical experts from 11 institutions. Key results of the intercomparison are: (1) a new, Certified Value for total carbon (TC) in SRM 1649a; (2) 14C Reference Values for total carbon and a number of organic species, including for the first time 8 individual PAHs; and (3) elemental carbon (EC) Information Values derived from 13 analytical methods applied to this component. Results for elemental carbon, which comprised a special focus of the intercomparison, were quite diverse, reflecting the confounding of methodological-matrix artifacts, and methods that tended to probe more or less refractory regions of this universal, but ill-defined product of incomplete combustion. Availability of both chemical and 14C speciation data for SRM 1649a holds great promise for improved analytical insight through comparative analysis (e.g., fossil/biomass partition in EC compared to PAH), and through application of the principle of isotopic mass balance.
Benzothiazole (BT), 2-hydroxybenzothiazole (HOBT), and 2-(4-morpholino)benzothiazole (24MoBT) leach from crumb rubber material (CRM) and asphalt containing 1-3% CRM. To determine whether benzothiazoles would be an environmental problem if roads containing CRM-modified asphalt (CMA) were built in the state of Rhode Island, the source and fate of these compounds were investigated. Benzothiazoles enter the environment from a number of sources such as the leaching of rubber products, fine particles of automobile tires, and antifreeze. Compared to the fluxes of benzothiazoles currently entering rivers from urban runoff, CMA roads may initially deliver substantially more benzothiazoles to the environment; however, with time this source may diminish as the road ages. Because the benzothiazoles are water soluble, it is unlikely that they will sorb to particles, settle to sediments, or be bioaccumulated. In addition, BT can be volatilized, and BT and HOBT can be microbially degraded. Therefore, the environmental chemistry of these compounds suggests that the inputs of benzothiazoles from CMA should not be harmful.
Abstract. The ratio of 37-carbon diunsaturated to diunsaturated and triunsaturated alkenones (uK'37) produced by some haptophytes is widely used as a proxy for past sea surface temperatures. However, our isothermal culturing experiments with Erniliania huxleyi clone CCMP372 show uK'37 values to also vary with nutrient availability and cell division rate. These results provide a reasonable explanation for large isothermal variation in uK'37 values of single coccolithophorid strains grown in culture. They also suggest that alkenone-based estimates of past sea surface temperatures may have been influenced by dissolved nutrient concentrations as well as by temperature.
Several physical and chemical parameters of sediment extraction and fractionation of organic compounds that influence bioassay results were evaluated. Each parameter was evaluated with a photoluminescent bacterial bioassay (Microtoxr̀) as an end point. Three solvents (acetonitrile, acetone, and methanol) were studied for their ability to extract toxic organic components from marine sediments. Acetone extracted the most toxicity, with no difference between acetonitrile and methanol. Two methods of fractionating sediment extracts (silica‐gel‐column chromatography [SGCC] and acid‐base fractionation) were compared. SGCC was more useful because it resulted in a wider range of responses and was faster to perform than acid‐base fractionation. Microtox was used to rank four marine sediments with respect to toxicity and to determine if one chemical class (or fraction) was consistently more toxic among different sediments. With some caveats, Microtox results agreed with general chemical concentration trends and other bioassay results in distinguishing between contaminated and noncontaminated sediments. Although results indicated there was not a consistently most toxic fraction among sediments, there was a consistently least toxic fraction. The effect of sediment storage time on toxicity was also evaluated. Results indicated that the most stable chemical fraction (containing nonpolar hydrocarbons) did not change toxicologically for 30 weeks, whereas the more chemically active fraction (containing ketones, quinones, and carboxyls) changed as soon as one week.
Measurements of the U K 0 37 index and the absolute abundance of alkenones in marine sediments are increasingly used in paleoceanographic research as proxies of past sea surface temperature and haptophyte (mainly coccolith-bearing species) primary productivity, respectively. An important aspect of these studies is to be able to compare reliably data obtained by different laboratories from a wide variety of locations. Hence the intercomparability of data produced by the research community is essential. Here we report results from an anonymous interlaboratory comparison study involving 24 of the leading laboratories that carry out alkenone measurements worldwide. The majority of laboratories produce data that are intercomparable within the considered confidence limits. For the
Geochemistry GeophysicsGeosystems G 3 G 3 rosell-melé et al.: alkenones interlaboratory comparison 2000GC000141measurement of alkenone concentrations, however, there are systematic biases between laboratories, which might be related to the techniques employed to quantify the components. The maximum difference between any two laboratories for any two single measurements of U K 0 37 in sediments is estimated, with a probability of 95%, to be <2.18C. In addition, the overall within-laboratory precision for the U K 0 37 temperature estimates is estimated to be <1.68C (95% probability). Similarly, from the analyses of alkenone concentrations the interlaboratory reproducibility is estimated at 32%, and the repeatability is estimated at 24%. The former is compared to a theoretical estimate of reproducibility and found to be excessively high. Hence there is certainly scope and a demonstrable need to improve reproducibility and repeatability of U
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