Assessing potential bioavailability of metals in sediments: A proposed approach

Due to anthropogenic inputs, elevated concentrations of metals frequently occur in aquatic sediments. In order to make defensible estimates of the potential risk of metals in sediments and/or develop sediment quality criteria for metals, it is essential to identify that fraction of the total metal in the sediments that is bioavailable. Studies with a variety of benthic invertebrates indicate that interstitial (pore) water concentrations of metals correspond very well with the bioavailability of metals in test sediments. Many factors may influence pore water concentrations of metals; however, in anaerobic sediments a key phase controlling partitioning of several cationic metals (cadmium, nickel, lead, zinc, copper) into pore water is acid volatile sulfide (AVS). In this paper, we present an overview of the technical basis for predicting bioavailability of cationic metals to benthic organisms based on pore water metal concentrations and metal-AVS relationships. Included are discussions of the advantages and limitations of metal bioavailability predictions based on these parameters, relative both to site-specific assessments and the development of sediment quality criteria.     

Effects of forest clearcutting in New England on stream macroinvertebrates and periphyton

Clearcutting may alter stream biota by changing light, temperature, nutrients, sediment particle size, or food in the stream. We sampled macroinvertebrates during late summer of 1979 in first and second order headwater streams draining both two- and three-year-old clearcuts and nearby uncut reference areas in northern New England, USA. Periphyton were sampled throughout the summer by placing microscope slides in these streams for 13–37 days. Periphyton cell densities on these slides following incubation were about six times higher in cutover than in reference streams. Green algae (Chlorophyceae) accounted for a higher proportion of total cell numbers in cutover than in reference streams, whereas diatoms (Bacillariophyceae) dominated the reference streams. The macroinvertebrate density in cutover streams was 2–4 times greater than that in the reference streams, but the number of taxa collected was similar in both cutover and reference streams. Higher numbers of mayflies (Ephemeroptera) and/or true flies (Diptera) in the cutover streams accounted for the differences. Because nutrient concentrations in the cutover streams were nearly the same as those in the reference streams, these differences in macroinvertebrate and periphyton densities were apparently caused by higher light levels and temperature in the streams in the clearcuts. Leaving buffer strips along streams will reduce changes in stream biology associated with clearcutting.Contribution from the Northeastern Forest Experiment Station, USDA Forest Service, Durham, New Hampshire 03824, USA.     

Biomass and nutrient removals from commercial thinning and whole-tree clearcutting of central hardwoods

The objective of this research was to evaluate the impacts of increasing product removal on biomass and nutrient content of a central hardwood forest ecosystem. Commercial thinning, currently the most common harvesting practice in southern New England, was compared with whole-tree clearcutting or maximum aboveground utilization. Using a paired-watershed approach, we studied three adjacent, first-order streams in Connecticut. During the winter of 1981–82, one was whole-tree clearcut, one was commercially thinned, and one was designated as the untreated reference. Before treatment, living and dead biomass and soil on the whole-tree clearcut site contained 578 Mg ha^–1 organic matter, 5 Mg ha^–1 nitrogen, 1 Mg ha^–1 phosphorus, 5 Mg ha^–1 potassium, 4 Mg ha^–1 calcium, and 13 Mg ha^–1 magnesium. An estimated 158 Mg ha^–1 (27% of total organic matter) were removed during the whole-tree harvest. Calcium appeared to be the nutrient most susceptible to depletion with 13% of total site Ca removed in whole-tree clearcut products. In contrast, only 4% (16 Mg ha^–1) of the total organic matter and 2% of the total nutrients were removed from the thinned site. Partial cuts appear to be a reliable management option, in general, for minimizing nutrient depletion and maximizing long-term productivity of central hardwood sites. Additional data are needed to evaluate the long-term impacts of more intensive harvests.     

The role of human capital,motivation and supervisor sponsorship in predicting career success

Based on Turner's (1960) contest‐ and sponsored‐mobility systems, a comprehensive model of the determinants of career success was examined. Human capital and motivational variables represented the contest‐mobility system whereas leader–member exchange and supervisor career mentoring represented the sponsored‐mobility system. Results based on data from 245 supervisor–subordinate dyads indicated limited support for the contest‐mobility system and strong support for the sponsored‐mobility system. Interestingly, the two forms of sponsorship were differentially related to career outcomes. Specifically, leader–member exchange was positively related to salary progression, promotability, and career satisfaction. Career mentoring, however, was only related to promotability. Copyright © 1999 John Wiley & Sons, Ltd.     

Field evaluation of a model for predicting nitrogen losses from drained lands

The N simulation model, DRAINMOD-N II, was field-tested using a 6-yr data set from an artificially drained agricultural site located in eastern North Carolina. The test site is on a nearly flat sandy loam soil which is very poorly drained under natural conditions. Four experimental plots, planted to a corn (Zea mays)-wheat (Triticum aestivum L.)-soybean (Glycine max.) rotation and managed using conventional and controlled drainage, were used in model testing. Water table depth, subsurface drainage, and N concentration in drain flow were measured and meteorological data were recorded continuously. DRAINMOD-N II was calibrated using the data from one plot; data sets from the other three plots were used for model validation. Simulation results showed an excellent agreement between observed and predicted nitrate-nitrogen (NO(3)-N) losses in drainage water over the 6-yr period and a reasonable agreement on an annual basis. The agreement on a monthly basis was not as good. The Nash-Sutcliffe modeling efficiency (EF) for monthly predictions was 0.48 for the calibration plot and 0.19, 0.01, and -0.02 for the validation plots. The value of the EF for yearly predictions was 0.92 for the calibration plot and 0.73, 0.62, and -0.10 for the validation plots. Errors in predicting cumulative NO(3)-N losses over the 6-yr period were remarkably small; -1.3% for the calibration plot, -8.1%, -2.8%, and 4.0% for the validation plots. Results of this study showed the potential of DRAINMOD-N II for predicting N losses from drained agricultural lands. Further research is needed to test the model for different management practices and soil and climatological conditions.     

Carbon supply and storage in tilled and nontilled soils as influenced by cover crops and nitrogen fertilization

Soil carbon (C) sequestration in tilled and nontilled areas can be influenced by crop management practices due to differences in plant C inputs and their rate of mineralization. We examined the influence of four cover crops {legume [hairy vetch (Vicia villosa Roth)], nonlegume [rye (Secale cereale L.)], biculture of legume and nonlegume (vetch and rye), and no cover crops (or winter weeds)} and three nitrogen (N) fertilization rates (0, 60 to 65, and 120 to 130 kg N ha(-1)) on C inputs from cover crops, cotton (Gossypium hirsutum L.), and sorghum [Sorghum bicolor (L.) Moench)], and soil organic carbon (SOC) at the 0- to 120-cm depth in tilled and nontilled areas. A field experiment was conducted on Dothan sandy loam (fine-loamy, siliceous, thermic Plinthic Paleudults) from 1999 to 2002 in central Georgia. Total C inputs to the soil from cover crops, cotton, and sorghum from 2000 to 2002 ranged from 6.8 to 22.8 Mg ha(-1). The SOC at 0 to 10 cm fluctuated with C input from October 1999 to November 2002 and was greater from cover crops than from weeds in no-tilled plots. In contrast, SOC values at 10 to 30 cm in no-tilled and at 0 to 60 cm in chisel-tilled plots were greater for biculture than for weeds. As a result, C at 0 to 30 cm was sequestered at rates of 267, 33, -133, and -967 kg C ha(-1) yr(-1) for biculture, rye, vetch, and weeds, respectively, in the no-tilled plot. In strip-tilled and chisel-tilled plots, SOC at 0 to 30 cm decreased at rates of 233 to 1233 kg C ha(-1) yr(-1). The SOC at 0 to 30 cm increased more in cover crops with 120 to 130 kg N ha(-1) yr(-1) than in weeds with 0 kg N ha(-1) yr(-1), regardless of tillage. In the subtropical humid region of the southeastern United States, cover crops and N fertilization can increase the amount of C input and storage in tilled and nontilled soils, and hairy vetch and rye biculture was more effective in sequestering C than monocultures or no cover crop.     

Preparation and FT-IR characterization of metal phytate compounds

Phytic acid (inositol hexaphosphoric acid, IP6) has long been recognized as the predominant organic P form in soil and animal manure. Whereas many studies have investigated the wet chemistry of IP6, there is little information on the characterization of solid metal IP6 compounds. This information is essential for further understanding and assessing the chemical behavior of IP6 in diverse soil-plant-water ecosystems. As the first step in full characterization, we synthesized eight metal phytate compounds and investigated their structural features using Fourier transform infrared spectroscopy (FT-IR). The absorption features from 900 to 1200 cm(-1) in FT-IR could be used to identify these phytates as: (i) light divalent metal (Ca and Mg) compounds with a sharp band and a broad band, (ii) heavy divalent metal (Cu and Mn) compounds with splitting broad bands, and (iii) trivalent metal (Al and Fe) compounds with a broad band and a shoulder band. Three different types of chemical structures of metal-phytate compounds were presented based on the FT-IR information. We further demonstrated that metal orthophosphates possessed different FT-IR spectral characteristics from their IP6 counterparts. The unique spectral features of metal phytates from 1000 to 700 cm(-1) could be used to distinguish phytate compounds from metal phosphate compounds. Thus, FT-IR analysis after fine tuning could provide an analytical tool to investigate the basic metal phytate chemistry in molecular levels, such as the competitive interactions between phosphate and phytate with a specific metal ion, and the conversion (or hydrolysis) of metal phytate to metal phosphate under various conditions.     

Quaternized agricultural by-products as anion exchange resins

The objectives of this study were the chemical modification of readily available, low-cost agricultural by-products to anion exchange resins and the selection of the best modified by-product for further use in anion removal. Resins were prepared through the quaternization of a series of 12 agricultural by-products with N-(3-chloro-2-hydroxypropyl) trimethylammonium chloride (CHMAC). Phosphate ion adsorption assays were conducted at pH 7 in order to compare adsorption properties among the by-products. Quaternized corn stover showed the highest phosphorus adsorption at 0.66 mmole/g. Since corn stover exhibited the best uptake of phosphate ion, it was compared to a commercially available, cellulose-based anion exchange resin. Additionally, adsorption capacities of quaternized corn stover for arsenate, chromate, and selenate were evaluated and adsorption efficiencies were determined in simulated wastewater samples. Our results indicate that modified corn stover demonstrates good adsorption uptake for arsenate and selenate and especially for chromate.     

A semipermeable membrane equilibrator for halomethanes in seawater

An equilibrator for sampling the partial pressures of halomethanes in seawater was designed and built, incorporating semipermeable membrane tubing to carry the gas phase. The equilibrator was tested for its ability to equilibrate chloromethane, bromomethane, iodomethane, and CFC-11. The residence time required for these halomethanes to equilibrate in the tubing (30 to 60 s) was determined experimentally. In a laboratory test, concentrations calculated from equilibrator measurements and based on published solubility values were found to differ by 6% to 16% from concentrations measured with a purge-and-trap apparatus, but uncertainties in the solubility values are likely to contribute significantly to the differences. In a comparison at sea, no significant difference was found between the semipermeable membrane equilibrator and another, more conventional equilibrator, except a 1.3% difference for CFC-11. This study demonstrates the feasibility of using semipermeable membranes in this and related applications.