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A. J. Horowitz

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

At least 19 recordsLinked to original sources

Determining annual suspended sediment and sediment-associated trace element and nutrient fluxes

Suspended sediment is a major factor in the biological and geochemical cycling of trace elements and nutrients in aquatic systems. The design of effective studies involving the collection, processing, and subsequent chemical analysis of suspended sediment requires a clear understanding of the problems associated with using this sample medium. This review summarizes the current state of knowledge relative to the various issues/problems associated with the collection of representative suspended sediment samples in fluvial systems. It also addresses issues associated with accurately determining the concentrations and fluxes of sediment-associated trace elements and nutrients.

Science of the Total Environment

The effects of land use on fluvial sediment chemistry for the conterminous U.S. - Results from the first cycle of the NAWQA Program: Trace and major elements, phosphorus, carbon, and sulfur

In 1991, the U.S. Geological Survey (USGS) began the first cycle of its National Water Quality Assessment (NAWQA) Program. The Program encompassed 51 river basins that collectively accounted for more than 70% of the total water use (excluding power generation), and 50% of the drinking water supply in the U.S. The basins represented a variety of hydrologic settings, rock types (geology), land-use categories, and population densities. One aspect of the first cycle included bed sediment sampling; sites were chosen to represent baseline and important land-use categories (e.g., agriculture, urban) in each basin. In total, over 1200 bed sediment samples were collected. All samples were size-limited (< 63????m) to facilitate spatial and/or temporal comparisons, and subsequently analyzed for a variety of chemical constituents including major (e.g., Fe, Al,) and trace elements (e.g., Cu, Zn, Cd), nutrients (e.g., P), and carbon. The analyses yielded total (??? 95% of the concentrations present), rather than total-recoverable chemical data. Land-use percentages, upstream underlying geology, and population density were determined for each site and evaluated to asses their relative influence on sediment chemistry. Baseline concentrations for the entire U.S. also were generated from a subset of all the samples, and are based on material collected from low population (??? 27??p km- 2) density, low percent urban (??? 5%), agricultural or undeveloped areas. The NAWQA baseline values are similar to those found in other national and global datasets. Further, it appears that upstream/underlying rock type has only a limited effect (mostly major elements) on sediment chemistry. The only land-use category that appears to substantially affect sediment chemistry is percent urban, and this result is mirrored by population density; in fact, the latter appears more consistent than the former.

Science of the Total Environment

Effects of hurricanes Katrina and Rita on the chemistry of bottom sediments in Lake Pontchartrain, Louisiana, USA

The effects of Hurricanes Katrina and Rita and the subsequent unwatering of New Orleans, Louisiana, on the sediment chemistry of Lake Pontchartrain were evaluated by chemical analysis of samples of street mud and suspended and bottom sediments. The highest concentrations of urban-related elements and compounds (e.g., Pb, Zn, polycyclic aromatic hydrocarbons, and chlordane) in bottom sediments exceeded median concentrations in U.S. urban lakes and sediment-quality guidelines. The extent of the elevated concentrations was limited, however, to within a few hundred meters of the mouth of the 17th Street Canal, similar to results of historical assessments. Chemical and radionuclide analysis of pre- and post-Hurricane Rita samples indicates that remobilization of near-shore sediment by lake currents and storms is an ongoing process. The effects of Hurricanes Katrina and Rita on the sediment chemistry of Lake Pontchartrain are limited spatially and are most likely transitory.

Environmental Science & Technology

The prediction of aquatic sediment-associated trace element concentration using selected geochemical factors

Multiple linear regression models calculated from readily obtainable chemical and physical parameters can explain a high percentage (70 per cent or greater) of observed sediment-trace element variance for Cu, Zn, Pb, Cr, Ni, Co, As, Sb, Se, and Hg in a widely divergent suite of 61 sediment samples. The independent variables used in the models may be single parameters, principal component scores, or principal component scores combined with their cross-products. The most useful type of variable must be determined on a case-by-case basis. The independent variables (geochemical parameters) incorporated in the models calculated during this study probably are applicable to many aquatic sediments; albeit, use of a larger data set (>61) could alter the magnitude of the calculated coefficients. The geochemical parameters included in the models were of a physical (e.g. grain size, surface area) and a chemical (e.g. organic matter, amorphous iron oxides) nature. Comparison between actual and predicted trace element concentrations obtained from the models may provide a means of defining ‘average’ sediment-trace element concentrations. In this context, the models may also help identify either naturally or anthropogenically impacted sites for additional study.

Hydrological Processes

The geochemistry of Seine River Basin particulate matter: Distribution of an integrated metal pollution index

Spatial analysis (1994-2001) and temporal trends (1980-2000) for particulate-associated metals at key stations in the Seine River Basin have been determined using a new metal pollution index (MPI). The MPI is based on the concentrations of Cd, Cu, Hg, Pb and Zn, normalized to calculated background levels estimated for each particulate matter samples for four fractions (clays and other aluminosilicates, carbonates, organic matter, and quartz). Background levels ascribed to each fraction were determined from a specific set of samples collected from relatively pristine areas in the upper Seine basin and validated on prehistoric samples. The unitless MPI is designed to vary between 0 for pristine samples to 100 for the ones extremely impacted by human activities and to assess the trends of general metal contamination and its mapping. Throughout the Seine basin, MPI currently range from 1 to 40, but values exceeding 100 have been found in periurban streams and the Eure tributary. Based on the MPI spatial distribution, the Seine River Basin displays a wide range of anthropogenic impacts linked to variations in population density, stream order, wastewater discharges and industrial activities. Correlations between the MPI and other trace elements indicate that anthropogenic impacts also strongly affect the concentrations of Ag, Sb, and P, marginally affect the concentrations of Ba, Ni, and Cr, and appear to have little effect on the concentrations of Li, Be, V, Co, and the major elements. Temporal MPI trends can also be reconstituted from past regulatory surveys. In the early 1980s, MPI were 2-5 times higher than nowadays at most locations, particularly downstream of Greater Paris where it reached levels as high as 250 (now 40), a value characteristic of present Paris urban sewage. The exceptional contamination of the Seine basin is gradually improving over the last 20 years but remains very high. ?? 2004 Elsevier B.V. All rights reserved.

Science of the Total Environment

Monitoring suspended sediment and associated trace element and nutrient fluxes in large river basins in the USA

In 1996, the US Geological Survey converted its occurrence and distribution-based National Stream Quality Accounting Network (NASQAN) to a national, flux-based water-quality monitoring programme. The main objective of the revised programme is to characterize large USA river basins by measuring the fluxes of selected constituents at critical nodes in various basins. Each NASQAN site was instrumented to determine daily discharge, but water and suspended sediment samples are collected no more than 12-15 times per year. Due to the limited sampling programme, annual suspended sediment fluxes were determined from site-specific sediment rating (transport) curves. As no significant relationship could be found between either discharge or suspended sediment concentration (SSC) and suspended sediment chemistry, trace element and nutrient fluxes are estimated using site-specific mean or median chemical levels determined from a number of samples collected over a period of years, and under a variety of flow conditions.

Conference Paper

Changes in sediment-associated trace element concentrations in the Seine river basin (1994-2001)

In the 1980's, based on the concentrations of particulate-associated Hg, Cd, Pb, Cu and Zn relative to very low natural background levels, the Seine River Basin was one of the most impacted in the world. Over the past 20 years, there has been a general decline in these elevated concentrations that parallels declines in Paris sewage sludge trace element levels. Within the basin, marked differences in spatial and temporal geochemical patterns have been observed: (1) between major tributaries, (2) between trace elements, and (3) with stream order and population density, all of which illustrate the complexity of the geochemical processes ongoing in the basin.

Conference Paper

Estimating suspended sediment and trace element fluxes in large river basins: Methodological considerations as applied to the NASQAN programme

In 1994, the NASQAN (National Stream Quality Accounting Network) programme was redesigned as a flux-based water-quality monitoring network for the Mississippi, Columbia, Colorado, and Rio Grande Basins. As the new programme represented a departure from the original, new sampling, processing, analytical, and data handling procedures had to be selected/developed to provide data on discharge, suspended sediment concentration, and the concentrations of suspended sediment and dissolved trace elements. Annual suspended sediment fluxes were estimated by summing daily instantaneous fluxes based on predicted suspended sediment concentrations derived from discharge-based log-log regression (rating-curve) models. The models were developed using both historical and current site-specific discharge and suspended sediment concentrations. Errors using this approach typically are less than ?? 10% for the 3-year reporting period; however, the magnitude of the errors increases substantially for temporal spans shorter than 1 year. Total, rather than total-recoverable, suspended sediment-associated trace element concentrations were determined by direct analysis of material dewatered from large-volume whole-water samples. Site-specific intra- and inter-annual suspended sediment-associated chemical variations were less (typically by no more than a factor of two) than those for either discharge or suspended sediment concentrations (usually more than 10-fold). The concentrations, hence the annual fluxes, for suspended sediment-associated phosphorus and organic carbon, determined by direct analyses, were higher than those determined using a more traditional paired, whole-water/filtered-water approach (by factors ranging from 1.5- to 10-fold). This may be important for such issues as eutrophication and coastal productivity. Filtered water-associated (dissolved) trace element concentrations were markedly lower than those determined during the historical NASQAN programme; many were below their respective detection limits. This resulted from the use of clean sampling, processing, and analytical protocols. Hence, the fluxes for filtered water-associated (dissolved) Ag, Pb, Co, V, Be, Sb, and Se, as well as the total (filtered water plus suspended sediment-associated) fluxes for these constituents, could not be estimated.

Hydrological Processes

Annual suspended sediment and trace element fluxes in the Mississippi, Columbia, Colorado, and Rio Grande drainage basins

Suspended sediment, sediment-associated, total trace element, phosphorus (P), and total organic carbon (TOC) fluxes were determined for the Mississippi, Columbia, Rio Grande, and Colorado Basins for the study period (the 1996, 1997, and 1998 water years) as part of the US Geological Survey's redesigned National Stream Quality Accounting Network (NASQAN) programme. The majority (??? 70%) of Cu, Zn, Cr, Ni, Ba, P, As, Fe, Mn, and Al are transported in association with suspended sediment; Sr transport seems dominated by the dissolved phase, whereas the transport of Li and TOC seems to be divided equally between both phases. Average dissolved trace element levels are markedly lower than reported during the original NASQAN programme; this seems due to the use of 'clean' sampling, processing, and analytical techniques rather than to improvements in water quality. Partitioning between sediment and water for Ag, Pb, Cd, Cr, Co, V, Be, As, Sb, Hg, and Ti could not be estimated due to a lack of detectable dissolved concentrations in most samples. Elevated suspended sediment-associated Zn levels were detected in the Ohio River Basin and elevated Hg levels were detected in the Tennessee River, the former may affect the mainstem Mississippi River, whereas the latter probably do not. Sediment-associated concentrations of Ag, Cu, Pb, Zn, Cd, Cr, Co, Ba, Mo, Sb, Hg, and Fe are markedly elevated in the upper Columbia Basin, and appear to be detectable (Zn, Cd) as far downstream as the middle of the basin. These elevated concentrations seem to result from mining and/or mining-related activities. Consistently detectable concentrations of dissolved Se were found only in the Colorado River Basin. Calculated average annual suspended sediment fluxes at the mouths of the Mississippi and Rio Grande Basins were below, whereas those for the Columbia and Colorado Basins were above previously published annual values. Downstream suspended sediment-associated and total trace element fluxes increase in the Mississippi and Columbia Basins, whereas fluxes markedly decrease in the Colorado Basin. No consistent pattern in trace element fluxes was detected in the Rio Grande Basin.

Hydrological Processes

The effect of mining and related activities on the sediment-trace element geochemistry of Lake Coeur d'Alene, Idaho, USA. Part III. Downstream effects: The Spokane River Basin

During 1998/1999, surface and subsurface sediment samples were collected along the entire length of the Spokane River from its outlet at the northern end of Lake Coeur d'Alene (CDA), Idaho, to Lake Roosevelt on the Columbia River, Washington. The study was conducted to determine if the trace element enrichments observed in Lake CDA and on the floodplain and in the CDA River extend through the Spokane River Basin (SRB). As in Lake CDA, surface sediments in the SRB are enriched in Pb, Zn, As, Cd, Sb and Hg relative to local background levels. Pb, Cd and Zn are the most elevated, with maximum enrichment occurring in the upper Spokane River in close proximity to Lake CDA. On average, enrichment decreases downstream, apparently reflecting both increased distance from the inferred source (the CDA River Basin), as well as increased dilution by locally derived but unenriched materials. Only Cd and Zn display marked enrichment throughout the SRB. Pb, Zn and Cd seem to be associated mainly with an operationally defined iron oxide phase, whereas the majority of the As and Sb seem to be matrix-held. Subsurface sediments also are enriched in Pb, Zn, As, Cd, Sb and Hg relative to background levels. Based on 137Cs and excess 210Pb dating, trace element enrichment began in the middle part of the SRB (Long Lake) between 1900 and 1920. This is contemporaneous with similar enrichments observed in Lake CDA, as well as the completion of Long Lake Dam (1913). In the most downstream part of the basin (Spokane River Arm of Lake Roosevelt), enrichment began substantially later, between 1930 and 1940. The temporal difference in enrichment between Long Lake and the River Arm may reflect the latter's greater distance from the presumed source of the enrichment (the CDA River Basin); however, the difference is more likely the result of the completion of Grand Coulee Dam (1934-1941), which formed Lake Roosevelt, backed up the Spokane River, and increased water levels in the River Armby about 30 m.

Hydrological Processes

Selected laboratory evaluations of the whole-water sample-splitting capabilities of a prototype fourteen-liter Teflon churn splitter

A prototype 14-L Teflon? churn splitter was evaluated for whole-water sample-splitting capabilities over a range of sediment concentratons and grain sizes as well as for potential chemical contamination from both organic and inorganic constituents. These evaluations represent a 'best-case' scenario because they were performed in the controlled environment of a laboratory, and used monomineralic silica sand slurries of known concentration made up in deionized water. Further, all splitting was performed by a single operator, and all the requisite concentration analyses were performed by a single laboratory. The prototype Teflon? churn splitter did not appear to supply significant concentrations of either organic or inorganic contaminants at current U.S. Geological Survey (USGS) National Water Quality Laboratory detection and reporting limits when test samples were prepared using current USGS protocols. As with the polyethylene equivalent of the prototype Teflon? churn, the maximum usable whole-water suspended sediment concentration for the prototype churn appears to lie between 1,000 and 10,000 milligrams per liter (mg/L). Further, the maximum grain-size limit appears to lie between 125- and 250-microns (m). Tests to determine the efficacy of the valve baffle indicate that it must be retained to facilitate representative whole-water subsampling.

Open-File Report

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

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

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