A Primer on Trace Metal- Sediment Chemistry

In most aquatic systems, concentrations of trace metals in suspended sediment and the top few centimeters of bottom sediment are far greater than concentrations of trace metals dissolved in the water column. Consequently, the distribution, transport, and availability of these constituents can not be intelligently evaluated, nor can their environmental impact be determined or predicted solely through the sampling and analysis of dissolved phases. This Primer is designed to acquaint the reader with the basic principles that govern the concentration and distribution of trace metals associated with bottom and suspended sediments. The sampling and analysis of suspended and bottom sediments are very important for monitoring studies, not only because trace metal concentrations associated with them are orders of magnitude higher than in the dissolved phase, but also because of several other factors. Riverine transport of trace metals is dominated by sediment. In addition, bottom sediments serve as a source for suspended sediment and can provide a historical record of chemical conditions. This record will help establish area baseline metal levels against which existing conditions can be compared. Many physical and chemical factors affect a sediment's capacity to collect and concentrate trace metals. The physical factors include grain size, surface area, surface charge, cation exchange capacity, composition, and so forth. Increases in metal concentrations are strongly correlated with decreasing grain size and increasing surface area, surface charge, cation exchange capacity, and increasing concentrations of iron and manganese oxides, organic matter, and clay minerals. Chemical factors are equally important, especially for differentiating between samples having similar bulk chemistries and for inferring or predicting environmental availability. Chemical factors entail phase associations (with such sedimentary components as interstitial water, sulfides, carbonates, and organic matter) and ways in which the metals are entrained by the sediments (such as adsorption, complexation, and within mineral lattices). INTRODUCTION The basic goal of most chemically oriented water-quality studies is to describe or evaluate existing environmental conditions and to attempt to identify the source or sources of the constituents under investigation. An equally important goal is to attempt to predict or determine potential impacts. This heading could accommodate such subjects as bioavailability, amount of constituent transport, location of chemical sinks, ultimate fate, and potential toxic effects. Historically, the U.S. Geological Survey has attempted to assess trace metals in aquatic systems by analyzing water samples. This assessment has entailed determining concentrations of total and dissolved elements and compounds through the collection and analysis, respectively, of unfiltered and filtered water. Concentrations associated with suspended sediment (particulates, seston) are determined indirectly by the difference between total and dissolved concentrations. It is recognized that this approach casts doubt on the reliability of reported suspended-sediment chemical analyses. As a result, water quality tends to be evaluated on the kinds and concentration of various constituents found in solution (Feltz, 1980). However, in most aquatic systems, the concentration of trace metals in suspended sediment and the top few centimeters of bottom sediment is far greater than the concentration of trace metals dissolved in the water column. The strong association of numerous trace metals (for example, As, Cd, Hg, Pb, Zn) with seston and bottom sediments means that the distribution, transport, and availability of these constituents can not be intelligently evaluated solely through the sampling and analysis of the dissolved phase. Additionally, because bottom sediments can act as a reservoir for many trace metals, they must, for several reasons, be given serious consideration in the planning and design of any water-quality study. First, an undisturbed sediment sink contains a historical record of chemical conditions. If a sufficiently large and stable sink can be found and studied, it will allow the investigator to study changes over time and, possibly, to establish area baseline levels against which existing conditions can be compared and contrasted. Second, under changing environmental or physicochemical conditions (like pH, Eh, dissolved oxygen, bacterial action), sediment-bound trace metals can dissolve into the water column, possibly enter the food chain, and have a significant environmental impact. Third, several relatively inert or otherwise environmentally harmless inorganic constituents can degrade, or react with others, to form soluble and potentially toxic forms (for example, the conversion of elemental mercury to methyl-mercury). Finally, bottom sediments should be regarded as a major, if not the major, source of suspended sediment. Therefore, they must be investigated to determine transport potential. Under changing hydrologic conditions (such as a heavy storm or spring runoff), a localized pollution problem can suddenly become widespread and result in significant environmental impact. The foregoing discussion indicates that data on suspended and bottom sediments, as well as on the dissolved phase, are a requisite for the development of a comprehensive understanding of the impact of trace metals on water quality. Through the use of such additional data, it may be possible to begin to identify sources and sinks and the fate and potential effects of toxic or environmentally necessary metals. Similarly, sediment-chemical data are a requisite for transport modeling, for estimating geochemical cycles, and for inferring the availability of various trace metals in an ecological system.