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Colleen E. Rostad

Publications and source records attributed to Colleen E. Rostad.

At least 19 recordsLinked to original sources

Biochar application to hardrock mine tailings: Soil quality, microbial activity, and toxic element sorption

Waste rock piles from historic mining activities remain unvegetated as a result of metal toxicity and high acidity. Biochar has been proposed as a low-cost remediation strategy to increase soil pH and reduce leaching of toxic elements, and improve plant establishment. In this laboratory column study, biochar made from beetle-killed pine wood was assessed for utility as a soil amendment by mixing soil material from two mine sites collected near Silverton, Colorado, USA with four application rates of biochar (0%, 10%, 20%, 30% vol:vol). Columns were leached seven times over 65 days and leachate pH and concentration of toxic elements and base cations were measured at each leaching. Nutrient availability and soil physical and biological parameters were determined following the incubation period. We investigated the hypotheses that biochar incorporation into acidic mine materials will (1) reduce toxic element concentrations in leaching solution, (2) improve soil parameters (i.e. increase nutrient and water holding capacity and pH, and decrease compaction), and (3) increase microbial populations and activity. Biochar directly increased soil pH (from 3.33 to 3.63 and from 4.07 to 4.77 in the two materials) and organic matter content, and decreased bulk density and extractable salt content in both mine materials, and increased nitrate availability in one material. No changes in microbial population or activity were detected in either mine material upon biochar application. In leachate solution, biochar increased base cations from both materials and reduced the concentrations of Al, Cd, Cu, Pb, and Zn in leachate solution from one material. However, in the material with greater toxic element content, biochar did not reduce concentrations of any measured dissolved toxic elements in leachate and resulted in a potentially detrimental release of Cd and Zn into solution at concentrations above that of the pure mine material. The length of time of effectiveness and specific sorption by biochar is variable by element and the toxic element concentration and acidity of the initial mine material.

Applied Geochemistry

Sorption of pure N 2 O to biochars and other organic and inorganic materials under anhydrous conditions

Suppression of nitrous oxide (N 2 O) emissions from soil is commonly observed after amendment with biochar. The mechanisms accounting for this suppression are not yet understood. One possible contributing mechanism is N 2 O sorption to biochar. The sorption of N 2 O and carbon dioxide (CO 2 ) to four biochars was measured in an anhydrous system with pure N 2 O. The biochar data were compared to those for two activated carbons and other components potentially present in soils—uncharred pine wood and peat—and five inorganic metal oxides with variable surface areas. Langmuir maximum sorption capacities ( Q max ) for N 2 O on the pine wood biochars (generated between 250 and 500 °C) and activated carbons were 17–73 cm 3 g –1 at 20 °C (median 51 cm 3 g –1 ), with Langmuir affinities ( b ) of 2–5 atm –1 (median 3.4 atm –1 ). Both Q max and b of the charred materials were substantially higher than those for peat, uncharred wood, and metal oxides [ Q max 1–34 cm 3 g –1 (median 7 cm 3 g –1 ); b 0.4–1.7 atm –1 (median 0.7 atm –1 )]. This indicates that biochar can bind N 2 O more strongly than both mineral and organic soil materials. Q max and b for CO 2 were comparable to those for N 2 O. Modeled sorption coefficients obtained with an independent polyparameter—linear free-energy relationship matched measured data within a factor 2 for mineral surfaces but underestimated by a factor of 5–24 for biochar and carbonaceous surfaces. Isosteric enthalpies of sorption of N 2 O were mostly between −20 and −30 kJ mol –1 , slightly more exothermic than enthalpies of condensation (−16.1 kJ mol –1 ). Q max of N 2 O on biochar (50000–130000 μg g –1 biochar at 20 °C) exceeded the N 2 O emission suppressions observed in the literature (range 0.5–960 μg g –1 biochar; median 16 μg g –1 ) by several orders of magnitude. Thus, the hypothesis could not be falsified that sorption of N 2 O to biochar is a mechanism of N 2 O emission suppression.

Environmental Science & Technology

An exploratory investigation of polar organic compounds in waters from a lead–zinc mine and mill complex

Surface water samples were collected in 2006 from a lead mine-mill complex in Missouri to investigate possible organic compounds coming from the milling process. Water samples contained relatively high concentrations of dissolved organic carbon (DOC; greater than 20 mg/l) for surface waters but were colorless, implying a lack of naturally occurring aquatic humic or fulvic acids. Samples were extracted by three different types of solid-phase extraction and analyzed by electrospray ionization/mass spectrometry. Because large amounts of xanthate complexation reagents are used in the milling process, techniques were developed to extract and analyze for sodium isopropyl xanthate and sodium ethyl xanthate. Although these xanthate reagents were not found, trace amounts of the degradates, isopropyl xanthyl thiosulfonate and isopropyl xanthyl sulfonate, were found in most locations sampled, including the tailings pond downstream. Dioctyl sulfosuccinate, a surfactant and process filtering aid, was found at concentrations estimated at 350 μg/l at one mill outlet, but not downstream. Release of these organic compounds downstream from lead-zinc mine and milling areas has not previously been reported. A majority of the DOC remains unidentified.

Missouri

Distribution of selected halogenated organic compounds among suspended particulate, colloid, and aqueous phases in the Mississippi River and major tributaries

Suspended particulate, colloid, and aqueous phases were separated and analyzed to determine spatial variation of specific organic compound transport associated with each phase in a dynamic river system. Sixteen sites along the Mississippi River and its major tributaries were sampled at low-flow conditions to maximize the possibility of equilibrium. Across the solubility range studied, the proportion transported by each phase depended on the compound solubility, with more water-soluble compounds (dacthal, trifluralin) transported predominantly in the aqueous phase and less-water soluble compounds (polychlorinated biphenyls, chlordane-related compounds) transported predominantly in the particulate and colloid phases.

Archives of Environmental Contamination and Toxico

Profiling refined hydrocarbon fuels using polar components

Identification of a fuel released into the environment can be difficult due to biodegradation or weathering. Negative electrospray ionization/mass spectrometry was used to screen for unique polar components in a wide variety of commercial hydrocarbon products and mixtures. These fuels produced unique and relatively simple spectra. When applied to hydrocarbon samples from a large, long-term fuel spill in a relatively cool climate in which the alkane, isoprenoid, and alkylcyclohexane portions had begun to biodegrade or weather, the polar components in these samples had changed little over time. This technique provided rapid fuel identification on hydrocarbons released into the environment, without sample preparation, fractionation, or chromatography.

Environmental Forensics

Studies on Disinfection By-Products and Drinking Water

Drinking water is disinfected with chemicals to remove pathogens, such as Giardia and Cryptosproridium, and prevent waterborne diseases such as cholera and typhoid. During disinfection, by-products are formed at trace concentrations. Because some of these by-products are suspected carcinogens, drinking water utilities must maintain the effectiveness of the disinfection process while minimizing the formation of by-products.

Fact Sheet

Discovery of cyanuric acid during an assessment of natural organic matter in stormflow water of the Santa Ana River, southern California, 2003-2004

A stormflow study of natural organic matter and organic contaminants in the Santa Ana River, the Mill Creek tributary, and an urban drain tributary discovered cyanuric acid in variable concentrations up to 510 g/L. Cyanuric acid was isolated with a hydrophilic natural organic matter (NOM) fraction, and its identity was confirmed by a combination of infrared spectrometry, 13C-nuclear magnetic resonance (13C-NMR) spectrometry, and electrospray ionization/mass spectrometry. Cyanuric acid concentrations, based upon 13C-NMR spectral quantitation, increased during the peak and recessional flows of the storm hydrographs during three storms at three sites. The greatest fluxes of cyanuric acid were observed in the Santa Ana River during the third storm. The most likely source of cyanuric acid is as a metabolite of triazine herbicides, based on hydrographs, land uses of the drainage basins, and the yearly application rates of triazine herbicides. The daily flux of cyanuric acid in Santa Ana River stormflow during the third storm was calculated to be about 1 percent of the yearly application rate for triazine herbicides. Cyanuric acid was not detected in ground water at wells adjacent to the Santa Ana River.

California

Kovats and lee retention indices determined by gas chromatography/mass spectrometry for organic compounds of environmental interest

Retention indices of standard organic compounds of environmental interest were determined by gas chromatography/mass spectrometry, using a DB‐5 fused‐silica capillary column. Retention indices are useful references for tentative compound identification by gas chromatography, or confirmation by gas chromatography/mass spectrometry. They provide elution order for isomers that might be indistinguishable based on mass spectra. Modified Kovats and Lee retention indices are given for polycyclic aromatic hydrocarbons; sulfur heterocycles; nitrogen heterocycles; aromatic amines; oxygen heterocycles; phenols; alcohols; ketones; alkanes; nitriles; and methylesters of fatty, dicarboxylic, and aromatic acids for comparison and reference. Retention index values for heterocycles by gas chromatography/mass spectrometry are comparable with gas chromatography values previously reported.

Journal of Separation Science

Screening of polar components of petroleum products by electrospray ionization mass spectrometry

The polar components of fuels may enable differentiation between fuel types or commercial fuel sources. Screening for these components in the hydrocarbon product is difficult due to their very low concentrations in such a complex matrix. Various commercial fuels from several sources were analyzed by flow injection analysis/electrospray ionization/mass spectrometry without extensive sample preparation, separation, or chromatography. This technique enabled screening for unique polar components at very low concentrations in commercial hydrocarbon products. This analysis was then applied to hydrocarbon samples collected from the subsurface with a different extent of biodegradation or weathering. Although the alkane and isoprenoid portion had begun to biodegrade or weather, the polar components had changed little over time. Because these polar compounds are unique in different fuels, this screening technique can provide source information on hydrocarbons released into the environment.

Energy and Fuels

Factors that affect molecular weight distribution of Suwannee river fulvic acid as determined by electrospray ionization/mass spectrometry

Effects of methylation, molar response, multiple charging, solvents, and positive and negative ionization on molecular weight distributions of aquatic fulvic acid were investigated by electrospray ionization/mass spectrometry. After preliminary analysis by positive and negative modes, samples and mixtures of standards were derivatized by methylation to minimize ionization sites and reanalyzed. Positive ionization was less effective and produced more complex spectra than negative ionization. Ionization in methanol/water produced greater response than in acetonitrile/water. Molar response varied widely for the selected free acid standards when analyzed individually and in a mixture, but after methylation this range decreased. After methylation, the number average molecular weight of the Suwannee River fulvic acid remained the same while the weight average molecular weight decreased. These differences are probably indicative of disaggregation of large aggregated ions during methylation. Since the weight average molecular weight decreased, it is likely that aggregate formation in the fulvic acid was present prior to derivatization, rather than multiple charging in the mass spectra.

Georgia

Organic contaminants associated with suspended sediment collected during five cruises of the Mississippi River and its principal tributaries, May 1988 to June 1990

Suspended-sediment samples were obtained from sites along the Mississippi River and its principal tributaries to determine the presence of halogenated hydrophobic organic compounds on the suspended sediment smaller than 63 micrometers. Sample collection involved pumping discharge-weighted volumes of river water along a cross section of the river into a continuous-flow centrifuge to isolate the suspended sediment. The suspended sediment was analyzed by gas chromatography/mass spectrometry for pentachlorobenzene, hexachlorobenzene, pentachloroanisole, chlorothalonil, pentachlorophenol, dachthal, chlordane, nonachlor, and penta-, hexa-, hepta-, and octachlorobiphenyls. Samples collected during June 1989 and February-March 1990 also were analyzed for U.S. Environmental Protection Agency priority pollutants, including polycyclic aromatic hydrocarbons, phthalate esters, and triazines. Samples were collected at sites on the Mississippi River from above St. Louis, Missouri to below New Orleans, Louisiana, and on the Illinois, Missouri, Ohio, Wabash, Cumberland, Tennessee, White, Arkansas, and Yazoo Rivers. Masses of selected halogenated hydrophobic organic compounds associated with the suspended sediment at each site are presented in this report in tabular format, along with suspended-sediment concentration, water discharge, and organic-carbon content.

Mississippi River

Cross sectional concentration data for selected organic contaminants in river waters near the confluence of the Mississippi River and the Illinois, Missouri, and Ohio Rivers, June 1989 and May-June 1990

Water samples were collected upstream and downstream from the confluence of the Ohio River and Mississippi River to study mixing of the river waters. Samples collected in June 1989 on the Mississippi River were analyzed for alachlor, atrazine, 2-chloro-2',6'-diethylacetanilide, cyanazine, desethyl-atrazine, desisopropylatrazine, 2,6-diethylaniline, 2-hydroxy-2',6'-diethylacetanilide, metolachlor, simazine, trimethyltriazinetrione, tris(2-chloroethyl) phosphate, and tris(chloroisopropyl) phosphate. Samples collected upstream and downstream from the confluence of the Ohio River and Mississippi River in May-June 1990 were analyzed for trimethyltriazinetrione, tris(2-chloroethyl) phosphate, and tris(chloroisopropyl) phosphate. Concentration data for six to fifteen locations across the rivers are presented in tabular form for two sites in 1989 and six sites in 1990.

Mississippi

Fractionation and characterization of organic matter in wastewater from a swine waste-retention basin

Organic matter in wastewater sampled from a swine waste-retention basin in Iowa was fractionated into 14 fractions on the basis of size (particulate, colloid, and dissolved); volatility; polarity (hydrophobic, transphilic, hydrophilic); acid, base, neutral characteristics; and precipitate or flocculates (floc) formation upon acidification. The compound-class composition of each of these fractions was determined by infrared and 13C-NMR spectral analyses. Volatile acids were the largest fraction with acetic acid being the major component of this fraction. The second most abundant fraction was fine particulate organic matter that consisted of bacterial cells that were subfractionated into extractable lipids consisting of straight chain fatty acids, peptidoglycans components of bacterial cell walls, and protein globulin components of cellular plasma. The large lipid content of the particulate fraction indicates that non-polar contaminants, such as certain pharmaceuticals added to swine feed, likely associate with the particulate fraction through partitioning interactions. Hydrocinnamic acid is a major component of the hydrophobic acid fraction, and its presence is an indication of anaerobic degradation of lignin originally present in swine feed. This is the first study to combine particulate organic matter with dissolved organic matter fractionation into a total organic matter fractionation and characterization.

Scientific Investigations Report

Tannins and terpenoids as major precursors of Suwannee River fulvic acid

Suwannee River fulvic acid (SRFA) was fractionated into 7 fractions by normal-phase chromatography on silica gel followed by reverse-phase fractionation on XAD-8 resin that produced 18 subfractions. Selected major subfractions were characterized by 13C-nuclear magnetic resonance (NMR), infrared spectrometry, and elemental analyses. 13C-NMR spectra of the subfractions were more indicative of precursor structures than unfractionated SRFA, and gave spectral profiles that indicated SRFA mass was about equally split between tannin precursors and terpenoid precursors. Lignin precursors were minor components. Synthesis of 13C-NMR data with elemental data for subfractions derived from both tannin and terpenoid precursors revealed high ring contents and low numbers of carbon per rings which is indicative of fused ring structures that are extensively substituted with carboxyl and methyl groups. These results ruled out extended chain structures for SRFA. This information is useful for determining sources and properties of fulvic acid in drinking water supplies as tannins are more reactive with chlorine to produce undesirable disinfection by-products than are terpenoids.

Scientific Investigations Report

Mass spectrometric identification of an azobenzene derivative produced by smectite-catalyzed conversion of 3-amino-4-hydroxyphenylarsonic acid

The compound 3-amino-4-hydroxyphenylarsonic acid (3-amino-HPAA) reacts with smectite to form a soluble azobenzene arsonic acid compound. This reaction is of particular interest because it provides a possible mechanism for the formation of a new type of arsenic compound in natural water systems. 3-Amino-HPAA is a degradation product excreted by chickens that are fed rations amended with roxarsone. Roxarsone is used to control coccidial intestinal parasites in most of the broiler chickens grown in the United States. The structure of the azobenzene arsonic acid compound was first inferred from negative-ion and positive-ion low-resolution mass-spectrometric analyses of the supernatant of the smectite suspension. Elemental composition of the parent ion determined by high-resolution positive-ion mass spectrometric measurements was consistent with the proposed structure of the azobenzene arsonic acid compound.

Talanta

Characterization of organic contaminants in environmental samples associated with Mount St. Helens 1980 volcanic eruption

Volcanic ash, surface-water, and bottom-material samples obtained in the vicinity of Mount St. Helens after the May 18, 1980, eruption were analyzed for organic contaminants by using capillary gas chromatography-mass spectrometry-computer techniques. Classes of compounds identified include n -alkanes, fatty acids, dicarboxylic acids, aromatic acids and aldehydes, phenols, resin acids, terpenes, and insect juvenile hormones. The most probable source of these compounds is from pyrolysis of plant and soil organic matter during and after the eruption. The toxicity of selected compounds and their environmental significance are discussed.

Washinton

Hydrologic setting and geochemical characterization of free-phase hydrocarbons in the alluvial aquifer at Mandan, North Dakota, November 2000

Free-phase hydrocarbons are present in the alluvial aquifer at Mandan, North Dakota. A large contaminant body of the hydrocarbons [light nonaqueous phase liquid (LNAPL)] floats on the water table about 20 feet below land surface. The main LNAPL body is about 6 feet thick, and the areal extent is about 657,000 square feet. A study was conducted to describe the hydrologic setting and characterize the geochemical composition of the free-phase hydrocarbons in the alluvial aquifer. Most of the study area is underlain by alluvium of the Heart River Valley that ranges in thickness from about 25 to 109 feet. The alluvium can be divided into three stratigraphic units silty clay, silty sand, and sand and is underlain by shales and sandstones. Monitoring wells were installed prior to this study, to an average depth of about 29 feet. Regional ground-water flow in the Heart River aquifer generally may be from west-northwest to eastsoutheast and is influenced by hydraulic connections to the river. Hydraulic connections also are probable between the aquifer and the Missouri River. Ground-water flow across the north boundary of the aquifer is minimal because of adjacent shales and sandstones of relatively low permeability. Recharge occurs from infiltration of precipitation and is spatially variable depending on the thickness of overlying clays and silts. Although the general water-table gradient may be from west-northwest to east-southeast, the flow directions can vary depending on the river stage and recharge events. Any movement of the LNAPL is influenced by the gradients created by changes in water-level altitudes. LNAPL samples were collected from monitoring wells using dedicated bailers. The samples were transferred to glass containers, stored in the dark, and refrigerated before shipment for analysis by a variety of analytical techniques. For comparison purposes, reference-fuel samples provided by the refinery in Mandan also were analyzed. These reference-fuel samples included a current diesel fuel, a closely related but slightly broader refinery-cut fuel, a crude-oil composite, unleaded regular gasoline, and additives. Four principal analytical techniques were used for geochemical characterization: Purge-and-trap gas chromatography/mass spectrometry (volatile components); capillary gas chromatography/mass spectrometry (semivolatile components); isotope ratio mass spectrometry (carbon isotopes; whole oils); and liquid chromatography/mass spectrometry with electrospray ionization (additives and other organic components). Volatile analytes included solvents, disinfection byproducts, halogenated hydrocarbons, and alkylbenzenes, including benzene, toluene, ethylbenzene, and meta-, para-, and orf/zo-xylenes. Semivolatile analytes included rt-alkanes, isoprenoid alkanes, cycloalkanes, and polycyclic aromatic hydrocarbons and related compounds (naphthalenes, phenanthrenes, and dibenzothiophenes and their alkylated derivatives). Of the additives, only the diesel-fuel additive with the red dye marker was amenable to electrospray ionization. Results indicate the LNAPL consists of closely correlatable diesel fuel at various stages of degradation. All LNAPL samples contained the red dye marker for diesel fuel. None of the samples contained chlorinated solvents associated with industries such as drycleaning or automotive maintenance. Solvents such as acetone, dimethyl ether, and methylene chloride and the gasoline additives methyl-t-butyl ether (MTBE), ethyl-t-butyl ether (ETBE), and t-amyl-methyl ether (TAME) were not found. With one possible exception, no evidence of a different diesel or other hydrocarbon fuel contribution was identified. At one site near the north edge of the main LNAPL body, evidence exists for traces of possible gasoline components in addition to the diesel fuel. The geochemical analysis of the LNAPL and correlations with other fuel products and additives strongly suggest episodic releases of a single, local-source, diesel fuel into the aquifer over an extended period of time.

North Dakota

Evaluation of lipid-containing semipermeable membrane devices for monitoring organochlorine contaminants in the Upper Mississippi river

Organochlorine contaminants sequestered in lipid-containing semipermeable membrane devices (SPMDs) were compared to those found in tangential-flow ultrafilter permeates as part of a pilot study at 10 sites in the Upper Mississippi River system. Caged and feral fish from three primary sites were also analyzed for comparison. Concentrated organochlorine (OC) compounds were readily extracted from the SPMDs by dialysis into hexane, and samples were analyzed by gas chromatography-negative chemical ionization-mass spectrometry. Fish and water samples were processed by conventional methods. Reasonable agreement was found between analyte SPMD-derived water concentrations and measured values of ultrafilter permeates; however, concentrations of the same analytes in caged fish did not appear to be proportional to water concentrations derived from SPMDs and ultrafilter permeates. The greatest number of OC compounds was detected in SPMDs; fewer were detected in caged fish and feral fish.

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