An analytical procedure involving sequential chemicai extractions has been developed for the partitioning of particulate trace metals (Cd, Co, Cu, Ni, Pb, Zn, Fe, and Mn) into five fractions: exchangeable, bound to carbonates, bound to Fe-Mn oxides, bound to organic matter, and residual. Experimental results obtained on replicate samples of fluvial bottom sediments demonstrate that the relative standard deviation of the sequential extraction procedure Is generally better than =10%. The accuracy, evaluated by comparing total trace metal concentrations with the sum of the five Individual fractions, proved to be satisfactory. Complementary measurements were performed on the Individual leachates, and on the residual sediments following each extraction, to evaluate the selectivity of the various reagents toward specific geochemical phases. An application of the proposed method to river sediments is described, and the resulting trace metal speciation is discussed.

Sequential extraction procedure for the speciation of particulate trace metals

Dead zones in the coastal oceans have spread exponentially since the 1960s and have serious consequences for ecosystem functioning. The formation of dead zones has been exacerbated by the increase in primary production and consequent worldwide coastal eutrophication fueled by riverine runoff of fertilizers and the burning of fossil fuels. Enhanced primary production results in an accumulation of particulate organic matter, which encourages microbial activity and the consumption of dissolved oxygen in bottom waters. Dead zones have now been reported from more than 400 systems, affecting a total area of more than 245,000 square kilometers, and are probably a key stressor on marine ecosystems.

Supporting Online Material for Spreading Dead Zones and Consequences for Marine Ecosystems

This book is written as a reference on organic substances in natural waters and as a supplementary text for graduate students in water chemistry. The chapters address five topics: amount, origin, nature, geochemistry, and characterization of organic carbon. Of these topics, the main themes are the amount and nature of dissolved organic carbon in natural waters (mainly fresh water, although seawater is briefly discussed). It is hoped that the reader is familiar with organic chemistry, but it is not necessary. The first part of the book is a general overview of the amount and general nature of dissolved organic carbon. Over the past 10 years there has been an exponential increase in knowledge on organic substances in water, which is the result of money directed toward the research of organic compounds, of new methods of analysis (such as gas chromatography and mass spectrometry), and most importantly, the result of more people working in this field. Because of this exponential increase in knowledge, there is a need to pull together and summarize the data that has accumulated from many disciplines over the last decade.

Organic geochemistry of natural waters

Over the past decade it has become apparent that the atmosphere is a significant pathway for the transport of many natural and pollutant materials from the continents to the ocean. The atmospheric input of many of these species can have an impact (either positive or negative) on biological processes in the sea and on marine chemical cycling. For example, there is now evidence that the atmosphere may be an important transport path for such essential nutrients as iron and nitrogen in some regions. In this report we assess current data in this area, develop global scale estimates of the atmospheric fluxes of trace elements, mineral aerosol, nitrogen species, and synthetic organic compounds to the ocean; and compare the atmospheric input rates of these substances to their input via rivers. Trace elements considered were Pb, Cd, Zn, Cu, Ni, As, Hg, Sn, Al, Fe, Si, and P. Oxidized and reduced forms of nitrogen were considered, including nitrate and ammonium ions and the gaseous species NO, NO2, HNO3, and NH3. Synthetic organic compounds considered included polychlorinated biphenyls (PCBs), hexachlorocyclohexanes (HCHs), DDTs, chlordane, dieldrin, and hexachlorobenzenes (HCBs). Making this assessment was difficult because there are very few actual measurements of deposition rates of these substances to the ocean. However, there are considerably more data on the atmospheric concentrations of these species in aerosol and gaseous form. Mean concentration data for 10° × 10° ocean areas were determined from the available concentration data or from extrapolation of these data into other regions. These concentration distributions were then combined with appropriate exchange coefficients and precipitation fields to obtain the global wet and dry deposition fluxes. Careful consideration was given to atmospheric transport processes as well as to removal mechanisms and the physical and physicochemical properties of aerosols and gases. Only annual values were calculated. On a global scale atmospheric inputs are generally equal to or greater than riverine inputs, and for most species atmospheric input to the ocean is significantly greater in the northern hemisphere than in the southern hemisphere. For dissolved trace metals in seawater, global atmospheric input dominates riverine input for Pb, Cd, and Zn, and the two transport paths are roughly equal for Cu, Ni, As, and Fe. Fluxes and basin-wide deposition of trace metals are generally a factor of 5-10 higher in the North Atlantic and North Pacific regions than in the South Atlantic and South Pacific. Global input of oxidized and reduced nitrogen species are roughly equal to each other, although the major fraction of oxidized nitrogen enters the ocean in the northern hemisphere, primarily as a result of pollution sources. Reduced nitrogen species are much more uniformly distributed, suggesting that the ocean itself may be a significant source. The global atmospheric input of such synthetic organic species as HCH,PCBs, DDT, and HCB completely dominates their input via rivers.

The atmospheric input of trace species to the world ocean

Recently, there has been growing interest in research into the role of plant-derived antioxidants in food and human health. The beneficial influence of many foodstuffs and beverages including fruits, vegetables, tea, coffee, and cacao on human health has been recently recognized to originate from their antioxidant activity. For this purpose, the most commonly methods used in vitro determination of antioxidant capacity of food constituents are reviewed and presented. Also, the general chemistry underlying the assays in the present paper was clarified. Hence, this overview provides a basis and rationale for developing standardized antioxidant capacity methods for the food, nutraceutical, and dietary supplement industries. In addition, the most important advantages and shortcomings of each method were detected and highlighted. The chemical principles of these methods are outlined and critically discussed. The chemical principles of methods of 2,2′-azinobis-(3-ethylbenzothiazoline-6-sulphonate) radical (ABTS·+) scavenging, 1,1-diphenyl-2-picrylhydrazyl (DPPH·) radical scavenging, Fe3+–Fe2+ transformation assay, ferric reducing antioxidant power (FRAP) assay, cupric ions (Cu2+) reducing power assay (Cuprac), Folin-Ciocalteu reducing capacity (FCR assay), peroxyl radical scavenging, superoxide anion radical (O
 2
 ·−
 ) scavenging, hydrogen peroxide (H2O2) scavenging, hydroxyl radical (OH·) scavenging, singlet oxygen (1O2) quenching assay and nitric oxide radical (NO·) scavenging assay are outlined and critically discussed. Also, the general antioxidant aspects of main food components were discussed by a number of methods which are currently used for detection of antioxidant properties food components. This review consists of two main sections. The first section is devoted to main components in the foodstuffs and beverages. The second general section is some definitions of the main antioxidant methods commonly used for determination of antioxidant activity of components in the foodstuffs and beverages. In addition, there are given some chemical and kinetic basis and technical details of the used methods.

Antioxidant activity of food constituents: an overview

Solubility of hydrous ferric oxide and iron speciation in seawater

Gulf Stream cold-core rings: Their physics, chemistry, and biology

The dimerization of (p-hydroxyphenyl)acetic acid by hydrogen peroxide in the presence of peroxidase has been adapted to the determination of hydrogen peroxide in seawater. The fluorometric method presented requires only one mixed reagent for sample analysis and produces a stable product that does not require immediate measurement. Changes in reaction stoichiometry resulting from naturally occurring organic material have been addressed. The detection limit, defined as 3 times the standard deviation of the blank, is 4 and 4 nM for open ocean and coastal seawater, respectively.

Hydrogen peroxide measurement in seawater by (p-hydroxyphenyl)acetic acid dimerization

Photochemical redox cycling of iron in coastal seawater

A series of leaching experiments designed to determine the soluble fraction of atmospheric iron in seawater was conducted. Aerosol samples collected in 1986 at four island stations (Midway, Oahu, Enewetak, and Fanning) of SEAREX (Sea-Air Exchange) and in May 1988 at station 4 (33.3°N, 139.1°W) of VERTEX (Vertical Transport and Exchange) were leached by surface seawater collected from the North Pacific and Sargasso Sea and at a pH range of 3–8. The results from these experiments indicated that for all marine aerosol samples examined, the dissolution of atmospheric iron was limited by a similar saturated concentration range. Using the operationally defined concept of a dissolved fraction that could pass through a 0.4-μm filter, the “saturated concentration” of dissolved atmospheric iron in seawater was found to be ∼10–17 nmol/kg. If 0.05-μm Millipore filter was used to separate the soluble fraction from the particulate fraction, the “saturated concentration” of dissolved atmospheric iron in seawater was found to be ∼5–8 nmol/kg. The dissolution of atmospheric iron in seawater takes place within a few minutes. If the total iron concentration was less than 2 nmol/kg (the open Pacific Ocean is in this category), ∼50% of the atmospheric iron dissolved in seawater. A comparison of the atmospheric dissolved iron flux into the North Pacific with the dissolved iron profile in this area suggests that more than 99% of the dissolved iron is provided by atmospheric input.

Dana R. Kester

Papers

Solubility of hydrous ferric oxide and iron speciation in seawater

Gulf Stream cold-core rings: Their physics, chemistry, and biology

Hydrogen peroxide measurement in seawater by (p-hydroxyphenyl)acetic acid dimerization

Photochemical redox cycling of iron in coastal seawater

The dissolution of atmospheric iron in surface seawater of the open ocean