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Abundant carbon substrates drive extremely high sulfate reduction rates and methane fluxes in Prairie Pothole Wetlands

Inland waters are increasingly recognized as critical sites of methane emissions to the atmosphere, but the biogeochemical reactions driving such fluxes are less well understood. The Prairie Pothole Region (PPR) of North America is one of the largest wetland complexes in the world, containing millions of small, shallow wetlands. The sediment pore waters of PPR wetlands contain some of the highest concentrations of dissolved organic carbon (DOC) and sulfur species ever recorded in terrestrial aquatic environments. Using a suite of geochemical and microbiological analyses, we measured the impact of sedimentary carbon and sulfur transformations in these wetlands on methane fluxes to the atmosphere. This research represents the first study of coupled geochemistry and microbiology within the PPR and demonstrates how the conversion of abundant labile DOC pools into methane results in some of the highest fluxes of this greenhouse gas to the atmosphere ever reported. Abundant DOC and sulfate additionally supported some of the highest sulfate reduction rates ever measured in terrestrial aquatic environments, which we infer to account for a large fraction of carbon mineralization in this system. Methane accumulations in zones of active sulfate reduction may be due to either the transport of free methane gas from deeper locations or the co-occurrence of methanogenesis and sulfate reduction. If both respiratory processes are concurrent, any competitive inhibition of methanogenesis by sulfate-reducing bacteria may be lessened by the presence of large labile DOC pools that yield noncompetitive substrates such as methanol. Our results reveal some of the underlying mechanisms that make PPR wetlands biogeochemical hotspots, which ultimately leads to their critical, but poorly recognized role in regional greenhouse gas emissions.

North Dakota

Using biotic ligand models to predict metal toxicity in mineralized systems

The biotic ligand model (BLM) is a numerical approach that couples chemical speciation calculations with toxicological information to predict the toxicity of aquatic metals. This approach was proposed as an alternative to expensive toxicological testing, and the U.S. Environmental Protection Agency incorporated the BLM into the 2007 revised aquatic life ambient freshwater quality criteria for Cu. Research BLMs for Ag, Ni, Pb, and Zn are also available, and many other BLMs are under development. Current BLMs are limited to ‘one metal, one organism’ considerations. Although the BLM generally is an improvement over previous approaches to determining water quality criteria, there are several challenges in implementing the BLM, particularly at mined and mineralized sites. These challenges include: (1) historically incomplete datasets for BLM input parameters, especially dissolved organic carbon (DOC), (2) several concerns about DOC, such as DOC fractionation in Fe- and Al-rich systems and differences in DOC quality that result in variations in metal-binding affinities, (3) water-quality parameters and resulting metal-toxicity predictions that are temporally and spatially dependent, (4) additional influences on metal bioavailability, such as multiple metal toxicity, dietary metal toxicity, and competition among organisms or metals, (5) potential importance of metal interactions with solid or gas phases and/or kinetically controlled reactions, and (6) tolerance to metal toxicity observed for aquatic organisms living in areas with elevated metal concentrations.

Applied Geochemistry

A multidisciplinary approach that considers occurrence, geochemistry, bioavailability, and toxicity to prioritize critical minerals for environmental research

Critical minerals (or critical elements) are minerals or elements that are essential to global security and development and have supply chains vulnerable to disruption. In general, knowledge of the environmental behavior and health effects of critical elements is needed to support the development of safe and environmentally responsible supplies. This knowledge includes identifying potential consequences of increased critical element production and use, alternative critical element sources such as mine wastes, and adverse effects of critical elements on ecosystem condition and organismal health. Here we identify significant data gaps in the understanding of critical elements in surficial and aquatic environments, and the need, given the large number of commodities (50) identified on the 2022 critical minerals list for the United States, for an approach to prioritize them for study of their environmental fate and effects. We propose a multidisciplinary approach for this prioritization, considering measures of occurrence, geochemistry, bioavailability, and toxicity. We describe relatively easy-to-obtain metrics for each of these topic areas and demonstrate the utility of this integrated prioritization approach using indium and zinc as examples. This approach facilitates prioritizing research with a focus on those critical elements that are most mobile in the environment, bioavailable, toxic, or simply lacking data in these categories.

Environmental Science & Technology

Cinnamon gulch revisited: Another look at separating natural and mining-impacted contributions to instream metal load

Baseline, premining data for streams draining abandoned mine lands is virtually non existent, and indirect methods for estimating premining conditions are needed to establish realistic, cost effective cleanup goals. One such indirect method is the proximal analog approach, in which premining conditions are estimated using data from nearby mineralized areas that are unaffected by mining. In this paper, we combine the proximal analog approach with a quantitative mass balance framework using data from a spatially-detailed synoptic sampling campaign. The combined approach is applied to Cinnamon Gulch, a headwater stream with numerous draining adits. Synoptic sampling results indicate that three of the top five metal sources are affected by mining activities, and stream segments draining these sources account for a large percentage of overall metal loading within the study reach. These initial calculations overestimate the effects of mining, as the affected stream segments were likely acidic and metal rich prior to mining. Premining loads and concentrations were therefore determined through a replacement approach in which the chemistry of each mining-affected stream segment is revised based on proximal analog concentrations. The revised loading profiles indicate that 15–17% of the Al, Cd, Cu, Mn, Ni, and Zn loads are attributable to mining, whereas the mining contribution for Pb is 40%. Premining concentrations of Al, Cd, Cu, Mn, and Zn are estimated to be in excess of aquatic life standards over the length of the study reach.

Colorado

Aliphatic structure of humic acids; a clue to their origin

Nuclear magnetic resonance spectra (both 1 H and 13 C) of humic acids from diverse depositional environments indicate the presence of aromatic chemical structures, most likely derived from lignin of vascular plants, and complex, paraffinic structures, most likely derived from algal or microbial sources. The latter components account for a major fraction of humic acid structures in both terrestrial and aquatic environments, suggesting that algae or microbes play a large role in humification of organic remains from both systems.

Organic Geochemistry

Stream-sediment geochemistry in mining-impacted streams: Prichard, Eagle, and Beaver Creeks, northern Coeur d'Alene mining district, northern Idaho

This report presents the results of one aspect of an integrated watershed-characterization study that was undertaken to assess the impacts of historical mining and milling of silver-lead-zinc ores on water and sediment composition and on aquatic biota in streams draining the northern part of the Coeur d'Alene Mining District in northern Idaho. We present the results of chemical analyses of 62 samples of streambed sediment, 19 samples of suspended sediment, 23 samples of streambank soil, and 29 samples of mine- and mill-related artificial- fill material collected from the drainages of Prichard, Eagle, and Beaver Creeks, all tributaries to the North Fork of the Coeur d'Alene River. All samples were sieved into three grain-size fractions (<0.063, 0.063-0.25, and 0.25-1.0 mm) and analyzed for 40 elements after four-acid digestion by inductively coupled plasma atomic-emission spectrometry and for mercury by continuous-flow cold-vapor atomic-absorption spectrometry in the U.S. Geological Survey laboratory in Denver, Colo. Historical mining of silver-lead-zinc ores in the headwater reaches of the Prichard Creek, Eagle Creek, and Beaver Creek drainages has resulted in enrichments of lead, zinc, mercury, arsenic, cadmium, silver, copper, cobalt, and, to a lesser extent, iron and manganese in streambed sediment. Using samples collected from the relatively unimpacted West Fork of Eagle Creek as representative of background compositions, streambed sediment in the vicinity of the mines and millsites has Pb and Zn contents of 20 to 100 times background values, decreasing to 2 to 5 times background values at the mouth of the each stream, 15 to 20 km downstream. Lesser enrichments (<10 times background values) of mercury and arsenic also are generally associated with, and decrease downstream from, historical silver-lead-zinc mining in the drainages. However, enrichments of arsenic and, to a lesser extent, mercury also are areally associated with the lode gold deposits along Prichard Creek near Murray, which were not studied here. Metal contents in samples of unfractionated suspended sediment collected during a high-flow event in April 2000 are generally similar to, but slightly higher than, those in the fine (<0.063-mm grain size) fraction of streambed sediment from the same sampling site. Although metal enrichment in streambed sediment typically begins adjacent to the mine portals and their associated mine-waste rock dumps, volumetrically larger inputs of metal-enriched materials were contributed by the ore-concentration millsites and their associated, more finely ground, more metal rich mill-tailings impoundments

Idaho

Molecular size of aquatic humic substances

Aquatic humic substances, which account for 30 to 50% of the organic carbon in water, are a principal component of aquatic organic matter. The molecular size of aquatic humic substances, determined by small-angle X-ray scattering, varies from 4.7 to 33 Å in their radius of gyration, corresponding to a molecular weight range of 500 to greater than 10,000. The aquatic fulvic acid fraction contains substances with molecular weights ranging from 500 to 2000 and is monodisperse, whereas the aquatic humic acid fraction contains substances with molecular weights ranging from 1000 to greater than 10,000 and is generally polydisperse.

Arizona, Colorado, Hawaii, Florida, Massachusetts,

Modeling and management of pit lake water chemistry 1: Theory

Pit lakes are permanent hydrologic/landscape features that can result from open pit mining for metals, coal, uranium, diamonds, oil sands, and aggregates. Risks associated with pit lakes include local and regional impacts to water quality and related impacts to aquatic and terrestrial ecosystems. Stakeholders rely on predictive models of water chemistry to prepare for and manage these risks. This paper is the first of a two part series on the modeling and management of pit lakes. Herein, we review approaches that have been used to quantify wall-rock runoff geochemistry, wall-rock leachate geochemistry, pit lake water balance, pit lake limnology (i.e. extent of vertical mixing), and pit lake water quality, and conclude with guidance on the application of models within the mine life cycle. The purpose of this paper is to better prepare stakeholders, including future modelers, mine managers, consultants, permitting agencies, land management agencies, regulators, research scientists, academics, and other interested parties, for the challenges of predicting and managing future pit lakes in un-mined areas.

Applied Geochemistry

Mineralogy and environmental geochemistry of historical iron slag, Hopewell Furnace National Historic Site, Pennsylvania, USA

The Hopewell Furnace National Historic Site in southeastern Pennsylvania, which features an Fe smelter that was operational in the 18th and 19th centuries, is dominated by three slag piles. Pile 1 slag, from the Hopewell Furnace, and pile 2 slag, likely from the nearby Cornwall Furnace, were both produced in cold-blast charcoal-fired smelters. In contrast, pile 3 slag was produced in an anthracite furnace. Ore samples from the nearby Jones and Hopewell mines that fed the smelter are mainly magnetite-rich with some sulfides (pyrite, chalcopyrite, sphalerite) and accessory silicates (quartz, garnet, feldspar, and clay minerals). Slag piles 1 and 2 are similar mineralogically containing predominantly skeletal and dendritic aluminian diopside and augite, skeletal forsteritic olivine, glass, rounded blebs of metallic Fe, and exotic quartz. Olivine is a major phase in all samples from pile 2, whereas it occurs in only a few samples from pile 1. Samples of the <2 mm-size fraction of surface composite slag material or crushed slag from at depth in piles 1 and 2 are mineralogically similar to the large surface slag fragments from those piles with the addition of phases such as feldspars, Fe oxides, and clay minerals that are either secondary weathering products or entrained from the underlying bedrock. Pile 3 slag contains mostly skeletal forsteritic olivine and Ti-bearing aluminian diopside, dendritic or fine-grained subhedral melilite, glass, euhedral spinel, metallic Fe, alabandite–oldhamite solid solution, as well as a sparse Ti carbonitride phase. The bulk chemistry of the slag is dominated by Al 2 O 3 (8.5–16.2 wt.%), CaO (8.2–26.2 wt.%), MgO (4.2–24.7 wt.%), and SiO 2 (36.4–59.8 wt.%), constituting between 81% and 97% of the mass of the samples. Piles 1 and 2 are chemically similar; pile 1 slag overall contains the highest Fe 2 O 3 , K 2 O and MnO, and the lowest MgO concentrations. Pile 3 slag is high in Al 2 O 3 , CaO and S, and low in Fe 2 O 3 , K 2 O and SiO 2 compared to the other piles. In general, piles 1 and 2 are chemically similar to each other, whereas pile 3 is distinct – a conclusion that reflects their mineralogy. The similarities and differences among piles in terms of mineralogy and major element chemistry result from the different smelting conditions under which the slag formed and include the fuel source, the composition of the ore and flux, the type of blast (cold versus hot), which affects the furnace temperature, and other beneficiation methods. The three distinct slag piles at Hopewell are enriched in numerous trace elements, such as As (up to 12 mg/kg), Cd (up to 0.4 mg/kg), Co (up to 31.8 mg/kg), Cu (up to 647 mg/kg), Mn (up to 0.69 wt.%), Pb (up to 172 mg/kg) and Zn (up to 393 mg/kg), together with Fe (13.9 wt.%), when compared to the average for the continental crust, with the <2 mm-size fraction commonly containing the highest concentrations. Enrichments in various elements (e.g., Cd, Co, Cu, Pb, Zn) were also found in the ore samples. Despite these enrichments, comparison of bulk chemistry trace-element concentrations to the environmental guidelines suggests most elements are likely not problematic with the exception of As, Co, Fe and Mn. Leachate tests that simulate weathering indicate Fe (up to 973 μg/L) and Mn (up to 133 μg/L) are readily released in potentially harmful concentrations compared to secondary drinking water and some aquatic ecosystem toxicity criteria. Aluminum and Cu, although not high in the solid compared to environmental guidelines, also exceed relevant criteria in leachate extracts with maximum concentrations of 2700 μg/L and 17.7 μg/L, respectively. In contrast, As and Co, which are significant in the solids, are not leached in concentrations that exceed guidelines (i.e., 3 μg/L or less for both elements). The weathering rates of the Fe metal and Fe oxides, which host Cu and some Fe, are likely higher than the silicate glass, which hosts the majority of Al, Mn and some Fe, and the crystalline silicates and spinels affecting which elements and how much are released into the environment and surrounding aquatic ecosystem. The mineral assemblages and their chemical composition, the bulk sample chemistry, and leachability of trace elements are all important components in understanding the potential environmental impacts of the slag piles.

Pennsylvania

Hydrogeologic framework, ground-water geochemistry, and assessment of nitrogen yield from base flow in two agricultural watersheds, Kent County, Maryland

Hydrostratigraphic and geochemical data collected in two adjacent watersheds on the Delmarva Peninsula, in Kent County, Maryland, indicate that shallow subsurface stratigraphy is an important factor that affects the concentrations of nitrogen in ground water discharging as stream base flow. The flux of nitrogen from shallow aquifers can contribute substantially to the eutrophication of streams and estuaries, degrading water quality and aquatic habitats. The information presented in this report includes a hydrostratigraphic framework for the Locust Grove study area, analyses and interpretation of ground-water chemistry, and an analysis of nutrient yields from stream base flow. An understanding of the processes by which ground-water nitrogen discharges to streams is important for optimal management of nutrients in watersheds in which ground-water discharge is an appreciable percentage of total streamflow. The U.S. Geological Survey, in cooperation with the U.S. Environmental Protection Agency (USEPA), collected and analyzed hydrostratigraphic and geochemical data in support of ground-water flow modeling by the USEPA. The adjacent watersheds of Morgan Creek and Chesterville Branch have similar topography and land use; however, reported nitrogen concentrations are generally 6 to 10 milligrams per liter in Chesterville Branch but only 2 to 4 milligrams per liter in Morgan Creek. Ground water in the surficial aquifer in the recharge areas of both streams has high concentrations of nitrate (greater than 10 milligrams per liter as N) and dissolved oxygen. One component of the ground water discharging to Morgan Creek typically is anoxic and contains virtually no dissolved nitrate; most of the ground water discharging to Chesterville Branch is oxygenated and contains moderately high concentrations of nitrate. The surficial aquifer in the study area is composed of the deeply weathered sands and gravels of the Pensauken Formation (the Columbia aquifer) and the underlying glauconitic sands of the upper Aquia Formation (the Aquia aquifer). The lower 6 to 9 meters of the Aquia Formation is a low-permeability silt-clay with abundant glauconite. The Aquia confining layer underlies the Columbia-Aquia surficial aquifer throughout the study area. The sediment redox transition, identified in cores, that occurs in the upper 0.5 to 1 meter of the Aquia confining layer is thought to be a site for subsurface denitrification of ground water. The first confined aquifer is composed of the glauconitic sands in the upper 9 to 11 meters of the Hornerstown Formation. The Hornerstown aquifer is underlain by 10 to 15 meters of glauconitic silt-clay at the base of the Hornerstown Formation (the Hornerstown confining layer), and 5 meters of low-permeability clay in the underlying Severn Formation. The Aquia and Hornerstown Formations dip and thicken to the southeast, and the Aquia confining layer subcrops shallowly (within 5 meters of the land surface) in a band that strikes southwest to northeast across the northern edge of the study area. The surficial aquifer is very thin (generally less than 5 meters) north of Morgan Creek, and the alluvial valley of Morgan Creek has incised into the top of the Aquia confining layer. In contrast, the Aquia confining layer lies 22 meters below Chesterville Branch, and the surficial aquifer approaches 30 meters in thickness (away from the creek). Chemically reduced iron sulfides and glauconite in the Aquia confining layer are likely substrates for denitrification of nitrate in ground water. Evidence from the dissolved concentrations of nitrate, sulfate, iron, argon, and nitrogen gas, and stable nitrogen isotopes support the interpretation that ground water flowing near the top of the Aquia confining layer, or through the confined Hornerstown aquifer, has undergone denitrification. This process appears to have the greatest effect on ground-water chemistry north of Morgan Creek, where the surficial aquifer is thin and a greater percentage of the ground water contacts the Aquia confining layer. The base-flow discharges of total nitrogen from the two watersheds are of similar magnitude, although Chesterville Branch has somewhat higher loads (29,000 kilograms of nitrogen per year) than Morgan Creek (20,000 kilograms of nitrogen per year), although Morgan Creek has a larger drainage area and a greater discharge of water. The base-flow yield of nitrogen (load per unit area) in Chesterville Branch (median of 0.058 grams per second per square kilometer at the outlet) is more than twice that of Morgan Creek (median of 0.022 grams per second per square kilometer at the outlet), reflecting the higher concentration of nitrate in ground water discharging to Chesterville Branch. Total nitrogen concentrations tend to decrease downstream in Chesterville Branch and increase downstream in Morgan Creek. The downstream trend in Chesterville Branch may be affected by instream nitrogen uptake and denitrification, and an increasing proportion of older, denitrified ground water in downstream discharge. The downstream trends in Morgan Creek may be affected by inflow from tributaries, downstream changes in the source of discharge water, and downstream changes in the riparian zone, which could affect the processes and degree of denitrification. Although these two watersheds appear to have landscape features (such as topography, land use, and soils) that would produce similar nitrogen discharges, a more detailed examination of landscape features indicates that Chesterville Branch has soils that are slightly better drained, tributary stream outlets at higher altitudes, and a slightly higher percentage of agricultural land. All of these factors have been related to higher nitrogen yields. Nonetheless, most of the data support the interpretation that hydrostratigraphy has the greatest effect in producing the difference in nitrogen yields between the two watersheds.

Maryland

Selenium source identification and biogeochemical processes controlling selenium in surface water and biota, Kendrick Reclamation Project, Wyoming, U.S.A.

The major tributaries draining the Kendrick Reclamation Project (KRP) account for an average of 52% of the total Se load measured in the North Platte River downstream from Casper, Wyoming. The Casper Creek drainage basin contributed the largest Se load of the five tributary sites to the North Platte River. The 4-d average Se concentration in water samples from one site in the part of the North Platte River that receives irrigation return flows exceeded the 5 μg/l U.S. Environmental Protection Agency's aquatic life criterion five time during a 50-d monitoring period in 1989. In agreement with the water-quality data, muscle and liver tissue rom rainbow trout collected from the same part of the North Platte River had Se concentrations exceeding levels known to cause reproductive failure and chronic Se poisoning. On the basis of Se: Cl, 18 O/ 16 O and D/H ratios in water from Goose and Rasmus Lee Lakes (closed-basin systems), the large Se concentrations in those lakes were derived by natural evaporation of irrigation water without leaching of soluble forms of Se from soil or rocks. Water samples from Thirtythree Mile Reservoir and Illco Pond (flow-through systems) showed considerable enrichment in Se over evaporative concentration, presumably due to leaching and desorption of Se from soil and rock. The Se: Cl ratios of irrigation drain water collected from the KRP indicate that leaching and desorption of soluble forms of Se from soils and rocks are the dominant processes in drain water. Results of a Wilcoxon matched-pairs test for 43 paired drain-water samples collected during June and August 1988, indicated there is a statistically larger concentration of Se (0.01 significance level) during the June sampling period. The larger concentrations of Se and other chemical constitutents during the early part of the irrigation season probably were due to dissolution of seleniferous salts that have accumulated in soils within the KRP since the last irrigation season. The large Se concentrations in water samples from wetland sites in the KRP were reflected in the aquatic-bird food chain. Most waterfowl and shorebirds nesting at the KRP showed Se concentrations in livers and eggs greater than levels suspected of causing adverse reproductive effects.

Wyoming

Characterization of dissolved organic materials in surface waters within the blast zone of Mount St Helens, Washington

After the May 18, 1980, eruption of Mount St Helens, the concentration of dissolved organic material in surface waters near the volcano increased significantly as a result of the destruction of the surrounding conifer forest. Low molecular weight organic compounds identified in the blast zone surface waters were derived from pyrolysis of plant and soil organic materials incorporated into pyroclastic flow, mud flow and debris avalanche deposits. A major fraction of the dissolved organic material consisted of high molecular weight, colored, organic acids that are similar in their general properties to aquatic fulvic acids found in more typical surface waters except for greater sulfur contents. The other major fraction of the dissolved organic material consisted of hydrophilic acids, which may include compounds capable of supporting heterotrophic microorganisms, and precursors in the formation of aquatic fulvic acids. The organic chemistry of blast zone surface waters will probably be greatly influenced by the May 18, 1980, eruption for many years.

Washington

Episodes of low dissolved oxygen indicated by ostracodes and sediment geochemistry at Crystal Lake, Illinois, USA

Low dissolved oxygen during the summer and early fall controls profundal continental ostracode distribution in Crystal Lake (McHenry County), Illinois, favoring Cypria ophthalmica and Physocypria globula at water depths from 6 to 13 m. These species also thrived in the lake's profundal zone from 14,165 to 9600 calendar year before present (cal yr b.p.) during the late Boiling, Allerod, and Younger Dryas chronozones, and early Holocene. Characterized by sand, cemented tubules, large aquatic gastropod shells, and littoral ostracode valves, thin (1-6 cm) tempestite deposits punctuate thicker deposits of organic gyttja from 16,080 to 11,900 cal yr b.p. The succeeding 2300 yr (11,900-9600 cal yr b.p.) lack tempestites, and reconstructed water depths were at their maximum. Deposition of marl under relatively well-oxygenated conditions occurred during the remainder of the Holocene until the arrival of Europeans, when the lake returned to a pattern of seasonally low dissolved oxygen. Such conditions are also indicated in the lake sediment by the speciation of phosphorus, high concentrations of organic carbon, and abundant iron and manganese occluded to mineral grains. Initial low dissolved oxygen was probably caused by the delivery of dissolved P and Fe in shallow groundwater, the chemistry of which was influenced by Spodosol pedogenesis under a spruce forest. The triggering may have been regionally warm and wet conditions associated with retreat of the Lake Michigan lobe (south-central Laurentide Ice Sheet). ?? 2010, by the American Society of Limnology and Oceanography Inc.

Limnology and Oceanography

Leaching characteristics of a high-calcium fly ash as a function of pH: A potential source of selenium toxicity

Using a modified extraction procedure, the effect of pH on the leaching of selected elements from Ca-rich (Type C) power plant fly ash was studied. Continuous additions of acetic acid were used to maintain pH values of fly ash slurries at 4.0, 6.0 and 8.0 for 24 h and an additional set was leached at its natural pH (average 11.8) value. Analyses for Se, As, Ca, Cd, Cr, Fe, Na and Pb showed that the highest concentrations occur in the leachate at pH 4.0 and decline with increasing pH. Concentrations of Cr and Fe increased slightly between neutral and high pH. Arsenic, Cd, Cr, Pb and Se concentrations exceeded the Environmental Protection Agency's toxicity criteria at pH 4.0. Selenium was above its toxicity level at pH values near 7 but the other elements were below their respective toxicity levels near neutral pH. Because recent studies show adverse effects of Se on aquatic life at far lower concentrations than the current Environmental Protection Agency's standard, high-Ca, power plant fly ashes represent a potentially hazardous pollutant to surface and subsurface waters.

Applied Geochemistry

Use of solid-state 13C NMR in structural studies of humic acids and humin from Holocene sediments

13 C NMR spectra of solid humic substances in Holocene sediments have been obtained using cross polarization with magic-angle sample spinning techniques. The results demonstrate that this technique holds great promise for structural characterizations of complex macromolecular substances such as humin and humic acids. Quantifiable distinctions can be made between structural features of aquatic and terrestrial humic substances. The aliphatic carbons of the humic substances are dominant components suggestive of input from lipid-like materials. An interesting resemblance is also noted between terrestrial humic acid and humin spectra.

Minnesota

Analytical results for Bullion Mine and Crystal Mine waste samples and bed sediments from a small tributary to Jack Creek and from Uncle Sam Gulch, Boulder River watershed, Montana

Metal-mining related wastes in the Boulder River basin study area in northern Jefferson County, Montana affect water quality as a result of acid-generation and toxic-metal solubilization. Mine waste and tailings in the unnamed tributary to Jack Creek draining the Bullion mine area and in Uncle Sam Gulch below the Crystal mine are contributors to water quality degradation of Basin Creek and Cataract Creek, Montana. Basin Creek and Cataract Creek are two of three tributaries to the Boulder River in the study area. The bed sediment geochemistry in these two creeks has also been affected by the acidic drainage from these two mines. Geochemical analysis of 42 tailings cores and eleven bed-sediment samples was undertaken to determine the concentrations of Ag, As, Cd, Cu, Pb, and Zn present in these materials. These elements are environmentally significant, in that they can be toxic to fish and/or the invertebrate organisms in the aquatic food chain. Suites of one-inch cores of mine waste and tailings material were taken from two breached tailings impoundments near the site of the Bullion mine and from Uncle Sam Gulch below the Crystal mine. Forty-two core samples were taken and divided into 211 subsamples. The samples were analyzed by ICP-AES (inductively coupled plasma-atomic emission spectroscopy) using a mixed-acid (HC1-HNO 3 -HC1O 4 -HF) digestion. Results of the core analyses show that some samples contain moderate to very high concentrations of arsenic (as much as 13,000 ppm), silver (as much as 130 ppm), cadmium (as much as 260 ppm), copper (as much as 9,000 ppm), lead (as much as 11,000 ppm), and zinc (as much as 18,000 ppm). Eleven bed-sediment samples were also subjected to the mixed-acid total digestion, and a warm (50°C) 2M HC1-1% H 2 O 2 leach and analyzed by ICP-AES. Results indicate that bed sediments of the Jack Creek tributary are impacted by past mining at the Bullion and Crystal mines. The contaminating metals are mostly contained in the 2M HC1-1% H 2 O 2 leachable phase, which are the hydrous amorphous iron- and manganese-hydroxide coatings on detrital sediment particles.

Montana

Relationship between peat geochemistry and depositional environments, Cranberry Island, Maine

The Heath, Great Cranberry Island, Maine, offers a unique locality for studying lateral and vertical relationships between radically different peat types within 1 km 2 . The majority of The Heath is a Sphagnum moss-dominated raised bog. Surrounding the raised bog is a swamp/marsh complex containing grass, sedge, Sphagnum moss, alder, tamarack, and skunk cabbage. Swamp/ marsh-deposited peat occurs both around the margins of The Heath and under Sphagnum -dominated peat, which was deposited within the raised bog. A third peat type, dominated by herbaceous aquatics, is present underlying the swamp/marsh-dominated peat but is not present as a dominant botanical community of The Heath. The three peat types have major differences in petrographic characteristics, ash contents, and associated minerals. Sulfur contents range from a low of 0.19 wt.% (dry) within the raised bog to a high of 4.44 wt% (dry) near the west end of The Heath, where swamp/marsh peat occurring directly behind a storm beach berm has been influenced by marine waters. The presence of major geochemical variations within a 1-km 2 peat deposit suggests the need for in-depth characterization of potential peat resources prior to use.

International Journal of Coal Geology

Comparison of XAD with other dissolved lignin isolation techniques and a compilation of analytical improvements for the analysis of lignin in aquatic settings

This manuscript highlights numerous incremental improvements in dissolved lignin measurements over the nearly three decades since CuO oxidation of lignin phenols was first adapted for environmental samples. Intercomparison of the recovery efficiency of three common lignin phenol concentration and isolation techniques, namely XAD, C 18 with both CH 3 OH (C 18 M) and CH 3 CN (C 18 A) used independently for priming and elution steps, and tangential flow filtration (TFF) for a range of aquatic samples including fresh, estuarine and marine waters, was undertaken. With freshwater samples XAD8-1, C 18 M and TFF were all observed to recover ca. 80–90% of the lignin phenols and showed no fractionation effects with respect to diagnostic lignin parameters. With estuarine and marine samples more lignin phenols were recovered with C 18 M and XAD8-1 than TFF because of the increased prevalence of low molecular weight lignin phenols in marine influenced samples. For marine systems, differences were also observed between diagnostic lignin parameters isolated via TFF vs. C 18 M and XAD8-1 as a result of the high molecular weight lignin phenols being less degraded than the bulk. Therefore, it is recommended for future studies of marine systems that only one technique is utilized for ease of intercomparison within studies. It is suggested that for studies solely aimed at recovering bulk dissolved lignin in marine environments that C 18 M and XAD8-1 appear to be more suitable than TFF as they recover more lignin. Our results highlight that, for freshwater samples, all three common lignin phenol concentration and isolation techniques are comparable to whole water concentrated by rotary evaporation (i.e. not isolated) but, that for marine systems, the choice of concentration and isolation techniques needs to be taken into consideration with respect to both lignin concentration and diagnostic parameters. Finally, as the study highlights XAD8-1 to be a suitable method for the isolation of dissolved lignin phenols from aquatic systems (statistically indistinguishable from C 18 M, P < 0.1), lignin data representative of whole waters can be produced for IHSS reference materials or other XAD sample archives.

Organic Geochemistry