Seed Clam Growth: An Alternative Sediment Bioassay Developed During EMAP in the Carolinian Province

A new sediment bioassay was developed in conjunction with EMAP studies conducted in the Carolinian Province using juvenile seed clams, Mercenaria mercenaria. This is a sublethal assay, based on growth (total dry weight) after a 7 day incubation period. Seed clam chronic growth assays were significantly more sensitive than amphipod acute toxicity assays. Optimization components include use of hatchery-reared juvenile clams in a rapid growth phase, and size-sieving to ensure a similar size range. Juvenile clam growth was not affected by sediment type, i.e., clams grew well in muddy and sandy sediments. Clams were slightly more sensitive to ammonia than amphipods (NOEC porewater total ammonia 14 - 16 mg/L for clams). Ammonia concentrations above these levels were more common in reference sites, so most of the false positives could be explained by ammonia toxicity. This assay possesses a number of other positive attributes that are desirable for a bioassay, including the requirement for a relatively small sample size (500 ml of sediments), balanced sensitivity, low incremental costs, and high information gained. The seed clam assay is believed to be a valuable tool for EMAP as well as other monitoring efforts for estimating potential chronic toxicity.     

Formation of volatile iodinated alkanes in soil: results from laboratory studies

Volatile iodinated organic compounds play an important role in the tropospheric photochemical system, but the current knowledge of the known sources and sinks of these alkyl iodides is still incomplete. This paper describes a new source of alkyl iodides from the pedosphere. Different organic-rich soils and humic acid were investigated for their release of volatile organoiodides. Six volatile organoiodides, iodomethane, iodoethane, 1-iodopropane, 2-iodopropane, 1-iodobutane and 2-iodobutane were identified and their release rates were determined. We assume an abiotic reaction mechanism induced by the oxidation of organic matter by iron(III). The influence of iron(III), iodide and pH on the formation of alkyl iodides was investigated. Additionally, different organic substances regarded as monomeric constituents of humus were examined for the production of alkyl iodides. Two possible reaction pathways for the chemical formation of alkyl iodides are discussed. As humic acids and iron(III) are widespread in the terrestrial environment, and the concentration of iodide in soil is strongly enriched (compared to seawater), this soil source of naturally occurring organoiodides is suggested to contribute significantly to the input of iodine into the troposphere.     

Methyl chloride emissions from halophyte leaf litter: dependence on temperature and chloride content

Methyl chloride (CH₃Cl) is the most abundant natural chlorine containing compound in the atmosphere, and responsible for a significant fraction of stratospheric ozone destruction. Understanding the global CH₃Cl budget is therefore of great importance. However, the strength of the individual sources and sinks is still uncertain. Leaf litter is a potentially important source of methyl chloride, but factors controlling the emissions are unclear. This study investigated CH₃Cl emissions from leaf litter of twelve halophyte species. The emissions were not due to biological activity, and emission rates varied between halophyte species up to two orders of magnitude. For all species, the CH₃Cl emission rates increased with temperature following the Arrhenius relation. Activation energies were similar for all investigated plant species, indicating that even though emissions vary largely between plant species, their response to changing temperatures is similar. The chloride and methoxyl group contents of the leaf litter samples were determined, but those parameters were not significantly correlated to the CH₃Cl emission rate.     

Release of methane from aerobic soil: an indication of a novel chemical natural process?

Methane (CH₄) formation under aerobic conditions has been intensely debated, especially since the discovery of CH₄ generation by both dried plant material and living plants. In this study we test the hypothesis that non-microbial CH₄ formation also occurs in soils. All lyophilised soil samples investigated under aerobic conditions released CH₄ at temperatures ranging from 30 to 70 °C exceeding that allowing normal enzymatic activity to proceed. No emissions were observed for single mineral soil components such as quartz sand, clay mineral and iron oxide. Methane release rates from the soils investigated were found to increase both with increasing temperature and higher organic carbon content. Addition of water to dried soils increased CH₄ release rates up to 8-fold those observed with the dried material. Our results suggest the existence of a chemical process in soils that produces CH₄ under aerobic conditions, a finding which has not been hitherto reported.     

Abiotic Fe(III) induced mineralization of phenolic substances

The redox process between iron(III) (in dissolved form and as the mineral phase ferrihydrite) and phenolic substances has been examined. We investigated the relationship between the structure and reactivity for the dihydrobenzene reductants catechol, hydroquinone and resorcine, and for the 2-methoxyphenol guaiacol with iron(III), by determining the rate of the Fe(III) reduction as well as the production of CO2. This work demonstrates that catechol and guaiacol will be effectively oxidized to CO2 by reducing iron(III). Hydroquinone shows a reduction of iron(III), but no accompanying mineralization could be determined. In contrast, resorcine showed no reaction with Fe(II). The deciding factor on whether or not mineralization occurs were controlled by the position of the hydroxy groups. It is shown that phenolic substances with two hydroxy groups in the orthoposition or at least one hydroxy group and a methoxy group can be oxidized to CO2 while iron(III) is reduced.