Edward T. Peltzer

The importance of atmospheric input of terrestrial organic material to deep sea sediments

The concentrations of lipids were determined in atmospheric particle, gas and rain samples collected from the tropical North Pacific to assess lipid sources, transport mechanisms and fluxes to the ocean surface. Four lipid compound classes (aliphatic hydrocarbons, fatty alcohols, fatty acid esters, and salts) all unequivocally show a terrestrial vascular plant source. These aerosol lipids originate from wind erosion of Asian and American soils and direct emission from vegetation. The major fluxes result from rain rather than dry deposition. These fluxes are large enough to have a major potential impact on the inventory of terrestrially derived lipid material found in deep-sea sediments. This has been showm for n-alkanes, fatty alcohols, fatty acids, total lipids and for organic carbon. By comparing atmospheric and sediment trap fluxes with sediment accumulation rates, it is suggested that some biogenic terrestrial material is more protected from degradation than marine-derived material.

The chemical conditions on the parent body of the murchison meteorite: Some conclusions based on amino, hydroxy and dicarboxylic acids

Amino and hydroxy acids have been identified in the Murchison meteorite. Their presence is consistent with a synthetic pathway involving aldehydes, hydrogen cyanide and ammonia in an aqueous environment (Strecker-cyanohydrin synthesis). From the various equilibrium and rate constants involved in this synthesis, four independent estimates of the ammonium ion concentrations on the parent body at the time of compound synthesis are obtained; all values are about 2 x 10(-3) M. Succinic acid and beta-alanine have also been detected in the Murchison meteorite. Their presence is consistent with a synthesis from acrylonitrile, hydrogen cyanide and ammonia. Using the equilibrium and rate constants for this synthetic pathway, and the succinic acid/beta-alanine ratio measured in the Murchison meteorite, an estimate of the hydrogen cyanide concentration of 10(-3) to 10(-2) M is obtained. Since hydrogen cyanide hydrolyzes relatively rapidly in an aqueous environment (t1/2 < 10(4) yrs) this high concentration implies a period of synthesis of organic compounds as short as 10(4) years on the Murchison meteorite parent body.

Enhanced lifetime of methane bubble streams within the deep ocean

We have made direct comparisons of the dissolution and rise rates of methane and argon bubbles experimentally released in the ocean at depths from 440 to 830 m. The bubbles were injected from the ROV Ventana into a box open at the top and the bottom, and imaged by HDTV while in free motion. The vehicle was piloted upwards at the rise rate of the bubbles. Methane and argon show closely similar behavior at depths above the methane hydrate stability field. Below that boundary (∼520 m) markedly enhanced methane bubble lifetimes are observed, and are attributed to the formation of a hydrate skin. This effect greatly increases the ease with which methane gas released at depth, either by natural or industrial events, can penetrate the shallow ocean layers.

Analyses of dissolved organic carbon in seawater: the JGOFS EqPac methods comparison

Abstract Results of a dissolved organic carbon (DOC) methods comparison are presented here in which five high temperature combustion (HTC) instruments and a wet chemical oxidation (WCO) method were used on a series of oceanic samples. The samples were collected during US JGOFS Equatorial Pacific Ocean cruises (EqPac) and most of the authors were involved with DOC analyses for the EqPac Program. Samples were collected with a “clean” protocol and were immediately quick frozen in replicate sample bottles. They were distributed by the first author to the other authors for “blind” analyses later on land on the stored samples. Comparable results (±7.5%) were found by three HTC instruments and the WCO method. There were difficulties with the other two HTC methods for which explanations and improvements are offered. The single most critical element for comparable DOC values appears to be assessment and subtraction of the total instrument blank (or reagent and handling blank for WCO methods). A “zero” carbon (very low C) water sample assisted in having all analysts achieve a uniform assessment of individual instrument or methods blanks. “Conditioning” of the catalyst bed in the combustion tube is critical to achieve consistent low instrument blanks. Failure to thoroughly condition the catalyst bed may be a significant error that can give erroneously high DOC values for oceanic samples. Reference standards available to all analysts also allowed comparison of instrument and methods performance. Contamination problems were demonstrated and it was shown that careful preparation and handling can reduce the potential for errors from contaminated samples. Results indicate that Equatorial Pacific oceanic DOC values in near surface waters are on the order of 60–70 μM C and deep water values on the order of 35–40 μM C. Since the “zero” carbon water contained a small, but measurable, amount of DOC, the sample values reported here may be slightly low. Because the lowest instrument blanks were equivalent to about 10 μM C, it is suggested that even if there were no instrument blank at all and all this “blank” were in the “zero” carbon water, the oceanic sample concentrations could not be underestimated by more than 10 μM C.

Spatial and temporal variability of total organic carbon along 140°W in the equatorial Pacific Ocean in 1992

Total organic carbon (TOC) was analyzed on four transects along 140°W in 1992 using a high temperature combustion/discrete injection (HTC/DI) analyzer. For two of the transects, the analyses were conducted on-board ship. Mixed-layer concentrations of organic carbon varied from about 80 μM C at either end of the transect (12°N and 12°S) to about 60 μM C at the equator. Total organic carbon concentrations decreased rapidly below the mixed-layer to about 38–40 μM C at 1000 m across the transect. Little variation was observed below this depth; deep water concentrations below 2000m were virtually monotonic at about 36 μM C. Repeat measurements made on subsequent cruises consistently found the same concentrations at 1000 m or deeper, but substantial variations were observed in the mixed-layer and the upper water column above 400 m depth. Linear mixing models of total organic carbon versus σθ exhibited zones of organic carbon formation and consumption. TOC was found to be inversely correlated with apparent oxygen utilization (AOU) in the region between the mixed-layer and the oxygen minimum. In the mixed-layer, TOC concentrations varied seasonally. Part of the variations in TOC at the equator was driven by changes in the upwelling rate in response to variations in physical forcing related to an El Nino and to the passage of tropical instability waves. TOC export fluxes, calculated from simple box models, averaged 8±4 mmol C m−2day−1 at the equator and also varied seasonally. These export fluxes account for 50–75% of the total carbon deficit and are consistent with other estimates and model predictions.

Final dissolved organic carbon broad community intercalibration and preliminary use of DOC reference materials

Abstract A broad community intercalibration exercise for accurate measurement of dissolved organic carbon (DOC) in seawater has been carried out over a period of 5 years. A set of 10 natural samples with DOC content from 40 to 200 μM C were accompanied by two glucose standards and a “zero C” blank; all sealed in glass ampoules. Samples were sent to all interested analysts for “blind” analysis; 62 laboratories in 17 countries participated. A total of 59 separate analyses were determined to be acceptable by screening criteria based on standards and blank; another nine sets of analyses did not pass the screening. The majority of the analyses, both those passing and those that did not, were performed with high temperature combustion (HTC) methods, six sets of analyses were done using wet chemical oxidation methods. From the 53 sets of acceptable HTC analyses, the coefficient of variation (%CV) for analytical comparability of the samples was 10% (“community precision”). It is estimated that the individual replicate injection precision for most instruments was approximately 2% and that no additional variability was caused by differences within the ampoules of individual samples. The additional variability over 2% was likely a result of both random and systematic differences in analytical capabilities from instrument to instrument and from day to day for individual instruments. With an arbitrary selection after the fact, smaller subsets of analysts can show comparability better than 10% and duplicate or triplicate runs on different days of the full sets of samples in several laboratories showed comparability in the 2–6.5% range. Experienced oceanic analysts, with internal or shared reference materials, can now show reproducibility and comparability at a level closer to 2%. Preliminary use of DOC reference materials by 14 participants showed day-to-day reproducibilities for their laboratories in the 2–6% range in most cases; several with poorer reproducibility do not normally perform DOC analyses on samples with concentrations as low as the deep ocean reference used here. Use of these reference materials can also give a demonstration of comparability between laboratories. For credibility of DOC analyses, it is necessary for analysts to use community reference materials and report results of their analytical performance with these references. This paper does not identify individual data nor should it be considered an evaluation of individual laboratories or analysts. The purpose is to show the summary picture of the international community of DOC analysts as it existed in the mid- to late 1990s.

A field study of the effects of CO2 ocean disposal on mobile deep-sea animals

Before the feasibility of ocean sequestration of anthropogenic carbon dioxide can be evaluated completely, there is a clear need to better understand the potential biological impacts of CO2-enriched (low pH and high pCO2) seawater in regions of proposed disposal. We describe here the first empirical study directly examining animal responses to dissolving CO2 hydrates on the deep-sea floor. Using a remotely operated vehicle (ROV) to conduct experiments within Monterey Canyon, CA, we found that several species (both invertebrate and vertebrate) did not avoid rapidly dissolving flocculent hydrates when attracted by the scent of food. Furthermore, while there were no apparent short-term effects of decreased pH, mobile animals appeared to suffer from respiratory distress due to increased pCO2 when in close proximity to hydrates. Losses of higher organisms as a result of CO2 disposal in the deep-sea may therefore be more extensive than previously predicted from toxicological models. However, the extent of changes to surrounding seawater chemistry, and thus biological impact, is largely dependent on CO2 release method or the type of hydrate formed.

A short-term in situ CO 2 enrichment experiment on Heron Island (GBR)

Ocean acidification poses multiple challenges for coral reefs on molecular to ecological scales, yet previous experimental studies of the impact of projected CO2 concentrations have mostly been done in aquarium systems with corals removed from their natural ecosystem and placed under artificial light and seawater conditions. The Coral–Proto Free Ocean Carbon Enrichment System (CP-FOCE) uses a network of sensors to monitor conditions within each flume and maintain experimental pH as an offset from environmental pH using feedback control on the injection of low pH seawater. Carbonate chemistry conditions maintained in the −0.06 and −0.22 pH offset treatments were significantly different than environmental conditions. The results from this short-term experiment suggest that the CP-FOCE is an important new experimental system to study in situ impacts of ocean acidification on coral reef ecosystems.

Some practical aspects of measuring DOC — sampling artifacts and analytical problems with marine samples

Abstract Efforts to reproduce the high-temperature catalytic oxidation technique for the determination of dissolved organic carbon (DOC) in marine samples are described and details of the construction of a home-made DOC analyzer are presented. Calibration of this instrument is compared with that of a commercial analzyer. Various problems relating to the determination of the instrument blank, instrument calibration, sample collection, preservation and processing are presented. Several hypotheses explaining the observed analytical artifacts are proposed and possible implications of these artifacts are discussed.

A comparison of methods for the measurement of dissolved organic carbon in natural waters

A small suite of natural samples spanning a wide range of DOC concentrations and salinities were analyzed by three high-temperature combustion (HTC) techniques and persulfate oxidation. One of the HTC techniques, sealed-tube combustion (STC), served as a referee method. Using this method, it was possible to obtain absolute DOC concentrations for the natural samples free of any analytical blank offset. Prior to the comparison of samples, an exchange of carbon-free water and calibration standards showed that all methods were equally well calibrated. Linear correlation analysis was used to differentiate whether the differences observed between methods was due to variable oxidation yields or to an artifact of the instrument blank. Agreement among the various methods was quite good, but yields for all methods decreased compared to the STC technique at concentrations of > 400 μM C. Persulfate results were found to be very similar to HTC results. Finally, carbon-free distilled water prepared by UVH2O2 oxidation or Milli-Q systems had near-zero DOC concentrations and was adequate for blank correction of all the various techniques yielding DOC concentrations in excellent agreement with the referee method.