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A. J. Horowitz

Publications and source records attributed to A. J. Horowitz.

At least 37 records · Page 2Linked to original sources

A study of porewater in water saturated sediments of levee banks and marshes in the lower Coeur d'Alene River valley, Idaho: Sampling, analytical methods, and results

This report contains information about the composition of interstitial porewater and solids from water saturated, metal contaminated levee banks at the river's edge and marshes in the lower Coeur d'Alene River valley. Data include pH, alkalinity, and concentrations of sulfate and metals (arsenic [As], cadmium [Cd], copper [Cu], iron [Fe], mercury [Hg], manganese [Mn], lead [Pb], antimony [Sb], and zinc [Zn]) in porewater and sulfur (S), carbon (C), and metal contents of associated solids. The results indicate that the pH of the porewater in all of the sediments is less than the pH of the Coeur d'Alene River. Dissolved concentrations of Mn and Fe are elevated in all of the porewater and levels of sulfate in porewater are below detection limits in almost all marsh sediments and in levee banks at the 2 sites furthest downstream. These observations suggest that levee bank and marsh sediments are suboxic or anoxic below the surface. Concentrations of dissolved Cd are greater in the Coeur d'Alene River than in porewater, while concentrations of As are greater in the porewater relative to the Coeur d'Alene River. Some concentrations of Cu, Pb, Sb, and Zn in porewater are lower, while others are higher, than dissolved concentrations in the Coeur d'Alene River. In addition, leaching experiments (i.e., Standard Elutriate Tests [SET]) were done in the laboratory to evaluate potential water quality impacts resulting from the addition of oxygen and water to these sediments. The intent of the experiments was to simulate how metal concentrations in water may be affected during dredging of contaminated sediments in the lower Coeur d'Alene River valley. The results indicate that there are releases of protons, sulfate, As, Mn, Pb, Sb, and Zn from the majority of levee bank and marsh sediments during leaching by Coeur d'Alene River water. At a water to sediment ratio of 4 to 1, most values of pH and dissolved concentrations of Cd, Fe, Pb, and Zn in the leaching solutions exceed the freshwater aquatic life standards for water of a hardness of 100 mg CaCOa/L. This work was funded by the U.S. EPA and was done to support their Remedial Investigation/Feasibility Study of the Coeur d'Alene and Spokane River basins.

Idaho↗

NASQAN: The design and implementation of a large-river suspended sediment and trace element flux programme

In 1996 the US Geological Survey (USGS) began a national flux-based water quality monitoring programme in the Mississippi, Columbia, Colorado, and Rio Grande basins. Suspended sediment flux estimates for periods greater than a year are generally accurate within ??15%. Discharge and suspended sediment concentrations varied much more than chemical levels. Most trace element concentrations are not elevated except Zn and Hg in the Ohio River, and Ag, Cu, Pb, Zn, Cd, Cr, Co, Ba, Mo, Sb, Hg, and Fe in the upper Columbia River, which is impacted by mining waste. The majority (???70%) of Cu, Zn, Cr, Ni, Ba, P, As, Fe, Mn, and Al are transported by suspended sediment; Sr transported seems dominated by the dissolved phase, whereas the transport of Li and TOC seem to be divided equally between both phases.In 1996 the US Geological Survey (USGS) began a national flux-based water quality monitoring programme in the Mississippi, Columbia, Colorado, and Rio Grande basins. Suspended sediment flux estimates for periods greater than a year are generally accurate within ??15%. Discharge and suspended sediment concentrations varied much more than chemical levels. Most trace element concentrations are not elevated except Zn and Hg in the Ohio River, and Ag, Cu, Pb, Zn, Cd, Cr, Co, Ba, Mo, Sb, Hg, and Fe in the upper Columbia River, which is impacted by mining waste. The majority (???70%) of Cu, Zn, Cr, Ni, Ba, P, As, Fe, Mn, and Al are transported by suspended sediment; Sr transported seems dominated by the dissolved phase, whereas the transport of Li and TOC seem to be divided equally between both phases.

Conference Paper↗

Variations in trace element geochemistry in the Seine River Basin based on floodplain deposits and bed sediments

Between 1990 and 1995 a series of bed sediment, suspended sediment and fresh floodplain samples were collected within the Seine River Basin, in France, to evaluate variations in trace element geochemistry. Average background trace element levels for the basin were determined from the collection and subsequent analyses of bed sediment samples from small rural watersheds and from a prehistoric (5000 BP) site in Paris. Concentrations are relatively low, and similar to those observed for fine-grained bed sediments from unaffected areas in the United States and Canada. However, the concentrations are somewhat higher than the reference levels presently adopted by French water authorities for areas north of the Seine Basin, which have similar bedrock lithologies. Downstream trace element variations were monitored in 1994 and 1995 using fresh surficial floodplain samples that were collected either as dried deposits a few days after peak discharge, or immediately after peak discharge (under ≤30 cm of water). Chemical comparisons between fresh floodplain deposits, and actual suspended sediments collected during flood events, indicate that, with some caveats, the former can be used as surrogates for the latter. The floodplain sediment chemical data indicate that within the Seine Basin, from the relatively unaffected headwaters through heavily affected urban streams, trace element concentrations vary by as much as three orders of magnitude. These trace element changes appear to be the result of both increases in population as well as concomitant increases in industrial activity. (This article is a US government work and is in the public domain in the United States.)

Hydrological Processes↗

Some thoughts on problems associated with various sampling media used for environmental monitoring

Modern analytical instrumentation is capable of measuring a variety of trace elements at concentrations down into the single or double digit parts-per-trillion (ng l-1) range. This holds for the three most common sample media currently used in environmental monitoring programs: filtered water, whole-water and separated suspended sediment. Unfortunately, current analytical capabilities have exceeded the current capacity to collect both uncontaminated and representative environmental samples. The success of any trace element monitoring program requires that this issue be both understood and addressed. The environmental monitoring of trace elements requires the collection of calendar- and event-based dissolved and suspended sediment samples. There are unique problems associated with the collection and chemical analyses of both types of sample media. Over the past 10 years, reported ambient dissolved trace element concentrations have declined. Generally, these decreases do not reflect better water quality, but rather improvements in the procedures used to collect, process, preserve and analyze these samples without contaminating them during these steps. Further, recent studies have shown that the currently accepted operational definition of dissolved constituents (material passing a 0.45 ??m membrane filter) is inadequat owing to sampling and processing artifacts. The existence of these artifacts raises questions about the generation of accurate, precise and comparable 'dissolved' trace element data. Suspended sediment and associated trace elements can display marked short- and long-term spatial and temporal variability. This implies that spatially representative samples only can be obtained by generating composites using depth- and width-integrated sampling techniques. Additionally, temporal variations have led to the view that the determination of annual trace element fluxes may require nearly constant (e.g., high-frequency) sampling and subsequent chemical analyses. Ultimately, sampling frequency for flux estimates becomes dependent on the time period of concern (daily, weekly, monthly, yearly) and the amount of acceptable error associated with these estimates.

Conference Paper↗

The effect of membrane filtration on dissolved trace element concentrations

The almost universally accepted operational definition for dissolved constituents is based on processing The almost universally accepted operational definition for dissolved constituents is based on processing whole-water samples through a 0.45-μm membrane filter. Results from field and laboratory experiments indicate that a number of factors associated with filtration, other than just pore size (e.g., diameter, manufacturer, volume of sample processed, amount of suspended sediment in the sample), can produce substantial variations in the ‘disolved’ concentrations of such elements as Fe, Al, Cu, Zn, Pb, Co, and Ni. These variations result from the inclusion/exclusion of colloidally-associated trace elements. Thus, 'dissolved' concentrations quantitated by analyzing filtrates generated by processing whole-water through similar pore-sized membrane filters may not be equal/comparable. As such, simple filtration through a 0.45-μm membrane filter may no longer represent an acceptable operational definition for dissolved chemical constituents. This conclusion may have important implications for environmental studies and regulatory agencies.

Water, Air, & Soil Pollution↗

Problems associated with using filtration to define dissolved trace element concentrations in natural water samples

Field and laboratory experiments indicate that a number of factors associated with filtration other than just pore size (e.g., diameter, manufacturer, volume of sample processed, amount of suspended sediment in the sample) can produce significant variations in the “dissolved” concentrations of such elements as Fe, Al, Cu, Zn, Pb, Co, and Ni. The bulk of these variations result from the inclusion/exclusion of colloidally associated trace elements in the filtrate, although dilution and sorption/desorption from filters also may be factors. Thus, dissolved trace element concentrations quantitated by analyzing filtrates generated by processing whole water through similar pore-sized filters may not be equal or comparable. As such, simple filtration of unspecified volumes of natural water through unspecified 0.45-μm membrane filters may no longer represent an acceptable operational definition for a number of dissolved chemical constituents.

Environmental Science & Technology↗

The effect of using different 0.45 μm filter membranes on 'dissolved' element concentrations in natural waters

The effect of 4 different 0.45 μm pore size filter membrane systems on the ‘dissolved’ concentration of 28 elements in 5 natural water samples of varying matrix is reported. In 3 of the 5 waters, consistently higher concentrations of most elements (minor and trace) are obtained using Nucleopore 47 mm filter and the cellulose acetate/nitrate 47 mm filter than those measured using the 142 mm cellulose nitrate MFS filter or the Gelman capsule 47 mm filter. These distinct and coherent patterns in elemental behaviour disappear for the other 2 samples, an organic-rich peat water of high suspended load and a mineralised sample high in Si and Ca. Thus the nature and degree of filtration artifacts is matrix-dependent. These trends are evident in both data sets produced by 2 independent laboratories using different instrumentation, techniques and calibrating procedures. The average relative standard deviation in elemental concentration across the 4 filter types is in the range 9–21%. The presence of such filtration artifacts must be considered in projects where, for example, seasonal variability of water composition is under examination, data from various sources are being merged or hydrogeochemical surveys are being conducted.

Applied Geochemistry↗

A summary of the effects of mining and related activities on the sediment-trace element geochemistry of Lake Coeur d'Alene, Idaho, USA

During 1989 and 1990 a series of 12 gravity cores, and 150 surface grab samples were collected in Lake Coeur d'Alene, Idaho to determine trace element concentrations, partitioning and surface and subsurface distribution patterns in the bed sediments of the lake. In addition, selected subsamples from one core were analyzed for 117 Cs activity to begin to establish a trace element geochemical history for the lake. The intent was to try and relate the trace element concentrations and distributions in the sediment column to past and present mining and mining related activities in the area. Substantial portions of the surface and near-surface sediments in Lake Coeur d'Alene are markedly enriched in Ag, As, Cd, Hg, Pb, Sb and Zn, and somewhat enriched in Cu, Fe and Mn. Surface distribution patterns, as well as variations in the thickness of the trace element-rich subsurface sediments, indicate that the source of much of this enriched material is the Coeur d'Alene River. The similarity between the trace element-rich surface and subsurface sediments with respect to: their location, their bulk chemistry, and their trace element partitioning indicate that the sources and/or concentrating mechanisms causing the trace element enrichment in the lake sediments probably have been the same throughout their depositional history. An estimated 75 million metric tons of trace element-rich sediments have been deposited on or in the lakebed. Based on a Mt. St. Helens' ash layer from the 1980 eruption, ages estimated from 137 Cs activity, and the presence of 80 discernible and presumably annual layers in a core collected near the Coeur d'Alene River delta, indicate that the deposition of trace element-rich sediments began, at least in the Coeur d'Alene River delta, some time between 1895 and 1910, dates consistent with the onset of mining and ore-processing activities that began in the area in the 1880's.

Journal of Geochemical Exploration↗

Scale as a factor in designing sampling programs for determination of annual trace element fluxes

Concentration data of suspended sediment-associated trace elements are a requisite for estimation of annual chemical fluxes. Fluvial suspended sediment and associated trace elements display marked shortterm spatial and temporal variability, suggesting that determination of annual fluxes requires high frequency depth and width integrated sampling and subsequent chemical analyses. When time scales are shifted from hours or days to a year, short-term variability is less important. A 2 year study on the Arkansas River indicates that it may be possible, after detailed site characterization of mean/median sediment chemical data, to estimate annual fluxes of trace elements solely through monitoring of discharge and suspended sediment concentration.

Effects of scale on interpretation and management ↗

The Effect of mining and related activities on the sediment-trace element geochemistry of Lake Coeur d'Alene, Idaho, U.S.A.; Part II, Subsurface sediments

During the summer of 1990, 12 gravity cores were collected in Lake Coeur d'Alene, Idaho, at various depths and in a variety of depositional environments. All core subsamples were analyzed to determine bulk chemistry and selected subsamples were analyzed for trace-element partitioning and (137)Cs activity. The purpose of these analyses was to determine the trace-element concentrations and distributions in the sediment column and to try to establish a trace-element geochemical history of the lake in relation to mining and mining-related discharge operations in the area. Substantial portions of the near-surface sediments in Lake Coeur d'Alene are markedly enriched in Ag, As, Cd, Hg, Pb, Sb, and Zn, and somewhat enriched in Cu, Fe, and Mn. Variations in the thickness of the trace element- rich sediments suggest that the source of much of this material is the Coeur d'Alene River. Calculated estimates indicate that there are some 75 million metric tons of trace element-rich sediments currently on/in the lakebed. Estimated trace-element masses in excess of those caused by non-mining-related sources, range from a high of 468,000 metric tons of Pb to a low of 260 metric tons of Hg. The similarity between the trace element-rich surface and subsurface sediments as regards their: (1) location; (2) bulk chemistry; (3) interelement relationships; and (4) trace-element partitioning indicate that the sources and/or concentrating mechanisms causing the trace-element enrichment in the lake probably have been the same throughout their depositional history. Based on Mt. St. Helens' ash layer from the 1980 eruption, ages estimated from (137)Cs activity, and the presence of 80 discernible and presumably annual layers in a core collected near the Coeur d'Alene River delta, it appears that deposition rates for the trace element-rich sediments varied from 2.1 to 1.3 cm/yr. These data also indicate that the deposition of trace element-rich sediments began, at least in the Coeur d'Alene River delta, sometime between 1895 and 1910, dates consistent with the onset of mining and ore-processing activities in the area which began in the 1880's.

Open-File Report↗

Effect of membrane filtration artifacts on dissolved trace element concentrations

Among environment scientists, the current and almost universally accepted definition of dissolved constituents is an operational one-only those materials which pass through a 0.45-μm membrane filter are considered to be dissolved. Detailed laboratory and field studies on Fe and Al indicate that a number of factors associated with filtration, other than just pore size, can substantially alter “dissolved” trace element concentrations; these include: filter type, filter diameter, filtration method, volume of sample processed, suspended sediment concentration, suspended sediment grain-size distribution, concentration of colloids and colloidally-associated trace elements and concentration of organic matter. As such, reported filtered-water concentrations employing the same pore size filter may not be equal. Filtration artifacts may lead to the production of chemical data that indicate seasonal or annual “dissolved” chemical trends which do not reflect actual environmental conditions. Further, the development of worldwide averages for various dissolved chemical constituents, the quantification of geochemical cycles, and the determination of short- or long-term environmental chemical trends may be subject to substantial errors, due to filtration artifacts, when data from the same or multiple sources are combined. Finally, filtration effects could have a substantial impact on various regulatory requirements.

Georgia↗

Use of sediment-trace element geochemical models for the identification of local fluvial baseline concentrations

Studies have demonstrated the utility of fluvial bed sediment chemical data in assesing local water-quality conditions. However, establishing local background trace element levels can be difficult. Reference to published average concentrations or the use of dated cores are often of little use in small areas of diverse local petrology, geology, land use, or hydrology. An alternative approach entails the construction of a series of sediment-trace element predictive models based on data from environmentally diverse but unaffected areas. Predicted values could provide a measure of local background concentrations and comparison with actual measured concentrations could identify elevated trace elements and affected sites. Such a model set was developed from surface bed sediments collected nationwide in the United States. Tests of the models in a small Louisiana basin indicated that they could be used to establish local trace element background levels, but required recalibration to account for local geochemical conditions outside the range of samples used to generate the nationwide models.

Conference Paper↗

Arsenopyrite in the bank deposits of the Whitewood Creek-Belle Fourche-Cheyenne River-Lake Oahe system, South Dakota, U.S.A.

Mining, milling, and processing wastes containing quantities of arsenopyrite were produced around Lead, South Dokata, from 1875 to 1977. Much of this material was discharged into Whitewood Creek, and from there portions of the waste were transported to the Belle Fourche River, thence to the Cheyenne River, and finally to the Missouri River. In 1958, the Missouri River was dammed at Pierre, forming Lake Oahe. Analyses of cores collected from the lake bottom showed the presence of arsenic-rich layers in the bed sediments; substantial portions of the arsenic are due to arsenopyrite in the 8-16 and 16-32 ??m size fractions of the sediments. In addition, suspended-sediment samples collected from the Cheyenne River above Lake Oahe contain detectable quantities of arsenopyrite in the 8-16 and 16-32 ??m fractions. Solid material collected from the banks and floodplains of the Belle Fourche River and Whitewood Creek contains reduced and oxidized phases. The reduced phases have arsenic maxima in the 16-32 and 32-63 ??m size ranges. These fractions also contribute the most arsenic to the samples; the major source being arsenopyrite. The oxidized segments have arsenic maxima in the < 2 and > 63 ??m size ranges. The < 2 ??m maxima are associated with widely disseminated, arsenic-bearing iron oxide coatings. However, the > 63 ??m fractions contribute the most arsenic to the oxidized samples. This arsenic, despite the oxidized nature of the samples, is associated with arsenopyrite coated with thin iron oxide rinds. It has been calculated that 80% of the arsenic in these deposits is associated with sulfides (in the form of arsenopyrite), while 20% is associated with iron oxides. The arsenopyrite found in the banks and floodplains of Whitewood Creek and the Belle Fourche River are the likely source of the arsenopyrite found in the suspended sediments of the Cheyenne River and in the bed sediment of Lake Oahe.

Conference Paper↗

The effect of mining on the sediment - trace element geochemistry of cores from the Cheyenne River arm of Lake Oahe, South Dakota, U.S.A.

Six cores, ranging in length from 1 to 2 m, were collected in the Cheyenne River arm of Lake Oahe, South Dakota, to investigate potential impacts from gold-mining operations around Lead, South Dakota. Sedimentation rates in the river arm appear to be event-dominated and rapid, on the order of 6-7 cm yr.-1. All the chemical concentrations in the core samples fall within the wide ranges previously reported for the Pierre Shale of Cretaceous age and with the exception of As, generally are similar to bed sediment levels in the Cheyenne River, Lake Oahe and Foster Bay. Based on the downcore distribution of Mn, it appears that reducing conditions exist in the sediment column of the river arm below 2-3 cm. The reducing conditions do not appear to be severe enough to produce differentiation of Fe and Mn throughout the sediment column in the river arm. Cross-correlations for high-level metal-bearing strata within the sediment column can be made for several strata and for several cores; however, cross-correlations for all the high-level metal-bearing strata are not feasible. As is the only element which appears enriched in the core samples compared to surface sediment levels. Well-crystallized arsenopyrite was found in high-As bearing strata from two cores and probably was transported in that form from reducing sediment-storage sites in the banks or floodplains of Whitewood Creek and the Belle Fourche River. It has not oxidized due to the reducing conditions in the sediment column of the Cheyenne River arm. Some As may also be transported in association with Fe- and Mn-oxides and -hydroxides, remobilized under the reducing conditions in the river arm, and then reprecipitated in authigenic sulfide phases. In either case, the As appears to be relatively immobile in the sediment column. ?? 1988.

Chemical Geology↗

The relation of stream sediment surface area, grain size and composition to trace element chemistry

Intensive studies of 17 geographically and hydrologically diverse stream bed sediments provide information on the relation between grain size, surface area, and operationally defined geochemical phases (e.g. Mn oxides, amorphous Fe oxides) to trace element concentrations. Of the size fractions investigated (<2, <16, <63and<125 μm), the strongest correlation with trace elements occurs with the percent <63 μm or<125 μm fractions. As the proportion of these size fractions increases in the samples, so do the trace element concentrations. When surface area (as defined by nitrogen adsorption and the BET equations) increases, trace element levels also increase. Correlations between bulk sediment chemistry and surface area are as strong as those between sediment chemistry and the proportion of the <63or<125 μm fractions. Surface area appears to serve as a proxy for grain size. The strongest correlations between grain size and surface area are the same as for trace elements and grain size (with the <63or<125 μm fractions). Surface area also is affected by geochemical phase, as are the trace elements associated with sediments. Of the phases considered (carbonates, Mn oxides, reactive Fe, amorphous Fe, organic matter), amorphous Fe oxides appear to exert the greatest control over both surface area and trace element levels. The concentrations of various geochemical phases affect surface area, grain size, and trace element chemistry. However, the effect of phase is grain-size dependent. For material with mean grain sizes in the fine sand range and coarser (> 125 μm), each of the various phases contribute to overall sample surface area. For material having mean grain sizes in the very fine sand range and finer (<125 μm), the same phases act as surface-area inhibitors by cementing fine grains together to form aggregates. This increases the mean grain size of the sample and reduces the surface area. The presence of these aggregates may explain why the <63 μm or<125 μm size fractions are more important to sediment-trace element levels and surface area than other finer fractions.

Applied Geochemistry↗