Geochemistry of peat over kimberlites in the Attawapiskat area, James Bay Lowlands, northern Canada

The James Bay Lowlands, which is the SE part of the Hudson Bay Lowlands, Canada, and within the Paleozoic limestone terrane, is covered mostly by peatlands. Peat samples were examined in the Attawapiskat area, a region of discontinuous permafrost, where more than 19 kimberlite pipes have been found beneath a cover of peat (2–4 m thick) and Quaternary sediments (up to 20 m thick) of Tyrell Sea clay beds and glacial tills. Pore water at a depth of 40 cm in the peat has a consistently low pH, <4, and high Eh, 290 mV, in the areas over limestones far from kimberlites. On the other hand, peat pore water close to kimberlites has a high pH, up to 6.7, and low Eh, down to 49 mV; the values of pH and Eh are inversely correlated. The high pH and low Eh close to kimberlites suggest active serpentinization of olivine in the underlying kimberlites. The bulk compositions of peat indicate precipitation of secondary CaCO₃ and Fe–O–OH. The secondary carbonate contains high concentrations of kimberlite pathfinder elements, such as Ni, rare earth elements (REE) and Y. The ratios of metal concentrations extracted by ammonium acetate solution at pH 5 (AA5) to those in a total digestion confirm that a majority of the divalent cations are hosted by the secondary carbonate, whereas tri-, tetra- and penta-valent cations are not. As these charged cations are not leached in Enzyme Leach, they are most likely adsorbed on Fe–O–OH.The compositions of peat show spatial variation with the distribution of kimberlites, suggesting that they are influenced by the underlying rocks even through there are thick layers of tills and sediments between the bedrocks and peat. However, elevated concentrations of pathfinder elements of kimberlites in bulk peat samples and AA5 leach are not necessarily directly above kimberlites. The diffused metal anomalies around kimberlites are attributed to the dissolution–precipitation of secondary phases (carbonates and Fe–O–OH) in acidic and reduced waters in peat, and the movement of waters through peat. This pilot study suggests that peat compositions do reflect the underlying bedrock compositions. For kimberlite exploration, a geochemical survey of peat is useful to discriminate concealed kimberlites from other anomalies defined by geophysical and other techniques; however, such a geochemical survey is not suitable for delineating the shapes of the concealed kimberlites due to broad dispersed anomalies.     

Palsa and peat plateau development in the Hudson Bay Lowlands, Canada: timing, pathways and causes

The Holocene development of a treed palsa bog and a peat plateau bog, located near the railroad to Churchill in the Hudson Bay Lowlands of northeastern Manitoba, was traced using peat macrofossil and radiocarbon analyses. Both sites first developed as wet rich fens through paludification of forested uplands around 6800 cal. yr BP. Results show a 20th-century age for the palsa formation and repeated periods of permafrost aggradation and collapse at the peat plateau site during the late Holocene. This timing of permafrost dynamics corroborates well with that inferred from previous studies on other permafrost peatlands in the same region. The developmental history of the palsa and peat plateau bogs is similar to that of adjacent permafrost-free fens, except for the specific frost heave and collapse features associated with permafrost dynamics. Permafrost aggradation and degradation is ascribed to regional climatic, local autogenic and other factors. Particularly the very recent palsa development can be assessed in terms of climatic changes as inferred from meteorological data and surface hydrological changes related to construction of the railroad. The results indicate that cold years with limited snowfall as well as altered drainage patterns associated with infrastructure development may have contributed to the recent palsa formation.     

Glacial dispersal of boulders in the James Bay Lowlands of Quebéc, Canada

Paleozoic fossiliferous limestones from the Hudson Bay area were dispersed southeastward a total distance of 110 km in the Québec part of theJames Bay Lowlands during the surging Cochrane flow event of the Laurentide Ice Sheet. The dispersal by the surging ice appears comparable to non-surging ice dispersal events elsewhere in terms of the dispersal index and the half distance of transportation; however, the total distance of transportation of the limestone clasts and their relatively high abundance far away from their source suggest that part of the transport of the debris during the surge was englacial, with the load later deposited as a surface mantle, or that the flow of the surging ice was limited to rapid basal sliding, with little or no internal shear within the ice mass. The glacial transport characteristics of earlier non-surging flow events in the same area were determined using the Total Transport Distance (TTD) method of measurements. Based on an indirect measurement of the half distance of transportation, the Selbaie till is characterized by longer transport distance than the Matheson till, and the Nouveau-Québec till has the shortest transport distance of all the tills of the area.     

Effects of photoirradiation on the adsorption of dissolved organic matter to goethite

The effects of photoirradiation of dissolved organic matter (DOM) on its subsequent adsorption to the Fe(III)oxyhydroxide mineral goethite were investigated at 22°C in 0.10 mol L⁻¹ NaClO₄ solutions at pH 3.5 and 5.5, Photoirradiation of DOM decreased the abundance of high molecular-weight components and formed new lower molecular-weight components, including low molecular weight carboxylic acids (i.e., formic, malonic, and acetic acids). Adsorption of non-irradiated DOM decreased from pH 3.5 to 5.5 and was dominated by the intermediate molecular weight (1251-3750 Da) fraction, although the 451-1250 and 3751-11350 Da fractions also contributed to adsorption at pH 3.5. Irradiation resulted in a substantial decrease in DOM adsorption affinity at pH 3.5, primarily due to loss of components in the 1251-3750 and 3751-11350 Da fractions. Irradiation resulted in only a small decrease in DOM adsorption affinity at pH 5.5; the loss of components in the 3751-11350 Da fraction upon irradiation had little effect on adsorption because they played little or no role in the non-irradiated sample at this pH. Irradiation of DOM also affected its interactions with Fe in solution and the solution iron(II)/iron(III) speciation. The combined effects of irradiation followed by adsorption produced DOM that was lower in molecular weight and had a decreased UV-Vis absorptivity than either process, alone. Together, these two processes are likely to have important environmental consequences in terms of UV penetration of surface waters, contaminant mobility, and DOM bioavailability.     

Holocene hydro-climatic change and effects on carbon accumulation inferred from a peat bog in the Attawapiskat River watershed,Hudson Bay Lowlands,Canada

Multiple proxies from a 319-cm peat core collected from the Hudson Bay Lowlands, northern Ontario, Canada were analyzed to determine how carbon accumulation has varied as a function of paleohydrology and paleoclimate. Testate amoeba assemblages, analysis of peat composition and humification, and a pollen record from a nearby lake suggest that isostatic rebound and climate may have influenced peatland growth and carbon dynamics over the past 6700 cal yr BP. Long-term apparent rates of carbon accumulation ranged between 8.1 and 36.7 g C m^? 2 yr^? 1 (average = 18.9 g C m^? 2 yr^? 1). The highest carbon accumulation estimates were recorded prior to 5400 cal yr BP when a fen existed at this site, however following the fen-to-bog transition carbon accumulation stabilized. Carbon accumulation remained relatively constant through the Neoglacial period after 2400 cal yr BP when pollen-based paleoclimate reconstructions from a nearby lake (McAndrews et al., 1982) and reconstructions of the depth to the water table derived from testate amoeba data suggest a wetter climate. More carbon accumulated per unit time between 1000 and 600 cal yr BP, coinciding in part with the Medieval Climate Anomaly.     

Spatial-seasonal dynamics of chromophoric dissolved organic matter in Lake Taihu, a large eutrophic, shallow lake in China

From 2005 to 2009, the spatial distribution and the seasonal dynamics of chromophoric dissolved organic matter (CDOM) were explored in Lake Taihu in eastern China. The spatial-seasonal dynamics of CDOM absorption and three CDOM composition variables, including spectral slope (S), spectral slope ratio (S_R) and the M value, defined as the ratio of absorption at 250 nm/365 nm, were analyzed and discussed. Furthermore, river input processes and degradation of phytoplankton were studied to assess their impact on CDOM composition and the factors involved in the spatial-seasonal variability of CDOM. The CDOM absorption coefficient at a wavelength of 350 nm, a(350), ranged from 1.37-9.55 m⁻¹ with a mean of 3.33 ± 1.32 m⁻¹. Spatially, higher a(350) values, but lower spectral slope, spectral slope ratio and M values, were recorded in the northern algae dominated bays while lower values were recorded in southeastern macrophyte dominated bays. The a(350) was significantly higher in inshore waters than in offshore waters. Values of S, S_R and M decreased during the flood and algal bloom season in spring and summer whereas a(350) increased. In the three river profiles, the gradual decrease of a(350) along the trajectory from the river mouth into the lake during the flood season showed the contribution of allochthonous CDOM. A laboratory phytoplankton degradation experiment was conducted to determine the contribution of CDOM production from phytoplankton. The significant increase of a(350) with time in the CDOM production experiment underlines the importance of autochthonous CDOM production during the algal bloom season. In summary, the significant increase of a(350) in spring and summer (algal bloom season) may be due to both the allochthonous CDOM input from the surrounding rivers and the autochthonous production of CDOM from degrading phytoplankton.     

Holocene carbon storage and testate amoeba community structure in treed peatlands of the western Hudson Bay Lowlands margin,Canada

The Hudson Bay Lowlands (HBL) stores a significant proportion of the northern peatland carbon pool, and constraints on the factors controlling local-scale variation are needed to better predict soil carbon stocks. We investigated two treed peatland sites, a fen and a bog, to understand how local ecohydrological factors impacted long-term carbon storage. Ecohydrological conditions were reconstructed using quantitative water table depth reconstructions from testate amoebae (TA) and broad peat type classifications. We also linked these factors and carbon storage to changes in TA community structure through the investigation of morphological and functional traits. Both sites have high rates of peat vertical accretion during the warmer Middle Holocene. A shift to a drier, Sphagnum-dominated habitat after 7400 cal a bp at the bog site, however, led to lower apparent carbon accumulation rates (aCARs) than at the fen site. aCARs decreased with the transition to a cooler Late Holocene climate at both sites. Both sites have higher total carbon masses (kg m⁻²) than other more open and younger HBL localities, demonstrating the potential importance of treed peatlands in regional carbon storage. Shifts in the frequency of TA traits corresponded to changing ecohydrological conditions and provided insights into the role of TA in carbon storage.     

The relative importance of chlorophyll and colored dissolved organic matter (CDOM) to the prediction of the diffuse attenuation coefficient in shallow estuaries

The availability of underwater light is a critical factor in the growth and abundance of primary producers in shallow embayments. The goal of this study was to examine the relative importance of factors influencing light availability in this type of water body. Many simulation models of aquatic ecosystems predict light attenuation from chlorophyll or phytoplankton stock. In the three southern New England sites studied here, no useful relationship was found to exist between chlorophyll and K_PAR (the diffuse attenuation coefficient of photosynthetically active radiation; Kirk 1994; Mobley 1994). In 40 of 53 cases, a regression of chlorophyll versus K_PAR was not statistically significant. Variation in K_PAR did demonstrate a correlation to salinity, implicating a freshwater source of light attenuating material. This was true even in a system with little freshwater inflow. Colored dissolved organic matter (CDOM) is one such terrestrial input that enters estuaries from their watersheds and can strongly influence the availability of light to aquatic primary producers. This study demonstrated that over 70% of the variability in the K_PAR coefficient can be attributed to CDOM in the shallow estuaries studied. This illustrates the need for improved model formulations that include CDOM in the prediction of light attenuation in shallow coastal systems. A new equation has been developed to predict K_PAR with CDOM.     

Diffusion and mass flow of dissolved carbon dioxide, methane, and dissolved organic carbon in a 7-m deep raised peat bog

In 65 samples, we got values (unusually replicable and consistent for this type of work) of concentration, ¹⁴C/¹³C (AMS) age, and δ¹³C for: peat, dissolved organic carbon (DOC), peat fractions, and dissolved CO₂ and CH₄ at 50-cm intervals down to 700 cm in Ellergower Moss, a rainwater-dependent raised (domed) bog in southwest Scotland. (1) We attribute the consistency of the results to Ellergower Moss being unusually homogeneous, with unusually low hydraulic conductivity, and containing only a few gas spaces; and to the sampling methods including 18-month equilibration of in situ samplers. (2) The dissolved gas concentration depth profiles are convex and very similar to each other, though CO₂ is 5-10 times more concentrated than CH₄, while the profile of DOC is concave. (3) The age profile of peat is near linearly proportional to depth; that for DOC is about 500-1000 yr younger than the peat at the same depth; the dissolved gases are 500-4300 years younger than the peat. The age of the operational peat fractions humic acid and humin is similar to that of whole peat. (4) The δ¹³C profile for deep peat is almost constant; δ¹³C-CO₂ is more enriched than the peat (δ¹³C-CO₂ 35‰ more); δ¹³C-CH₄ is the same amount more depleted. Nearer the surface both dissolved gases become steadily more depleted, δ¹³C is about 20‰ less at the surface. (5) A simulation shows that mass flow can account for the concentration and age profiles of DOC, but for the gases diffusion and an additional source near the surface are needed as well, and diffusion accounts for over 99% of the dissolved gas movements. (6) The same processes must operate in other peatlands but the results for Ellergower should not be extrapolated uncritically to them.     

Emergent coasts of Akimiski Island,James Bay,Northwestern Territories,Canada: geology,geomorphology, and vegetation

Akimiski Island contains good examples of emergent coastal landscapes of a cold mesotidal inland sea. The Paleozoic reefal trend of the Attawapiskat Formation dictated the overall shape and the main structure of the island. Differential erosion and deposition by Pleistocene glaciers have fluted the island in a north-south direction. That surface was later modified by emergent landforms developed in the last 3500–4000 yrs.The modern steeper southern area reaches an elevation of 60 m approximately 3 km inland from the southern shoreline, and contains well-developed sandy and gravelly longitudinal beach ridges and spits, now inactive and covered by a lichen-rich taiga (boreal forest). The flatter, northern part of the island shows a wide transition between the primarily erosional, sand-starved, coastal marshland and the inland organic-rich fens. Partially paludified longitudinal and transversal beach ridges subdivide those northern flat wetlands forcing a straight course to the north-flowing streams.The vegetation zonations of the marshes are as varied as the coasts, facing different oceanographic conditions. Longshore and tidal currents affect the western and southern coasts greatly. Tides, waves and sea ice affect the others more. The marshes resemble those of the mainland in having well-defined Puccinellia phryganodes lower marsh, Carex subspathacea upper marsh, and peat-forming coastal fens. Some components of the marshes of the island, such as isolated mounds with vegetation minisequences, incipient permafrost features generated by seasonal frozen ground conditions, and intense grazing by large populations of geese, are typical of cold settings, more commonly found along mainland coasts farther to the north in James Bay and Hudson Bay.     

Optical characteristics and solar photodegradation of dissolved organic matter in Arkansas River, USA

Dissolved organic matter （DOM）, a mixture of numerous organic compounds of 30 to 300000 D, exists in all natural water resources including rivers, lakes and oceans, and plays a very important role in global carbon cycle and ecology. The DOM molecules absorb UV light strongly in short wavelengths and prevent microorganisms from being damaged by solar UV irradiation. Meanwhile, the large DOM molecules are then photodegraded into inorganic carbon and smaller organic molecules which are easier for bacterioplankton to digest. The Arkansas River is one of the largest rivers in the US, and a major input of organic materials to the Mississippi River and Gulf of Mexico. However, the photochemical properties of the DOM in the river water have not been investigated. To study this photodegradation process of the Arkansas River, water samples from the river were collected, filtered, sealed into quartz flasks, and exposed to sunlight for up to 15 hours. Some samples were retrieved from the flasks at certain time intervals. The intensity of the sunlight was measured during the exposure process at 30 min to 1 hr intervals. UV-vis absorption, fluorescence emission, 3D fluorescence spectra and DOM concentrations were determined for all retrieved samples. It was found that the total DOM concentration decreased while the dissolved inorganic carbon （DIC） concentration increased in the samples. UV absorption and fluorescence intensity of DOM decreased exponentially. The disappearance rate of UV absorption varied with wavelength. The loss of integral fluorescence was about 2.6 times that of the UV absorption at the excitation wavelength. In addition, the quantum yields also decreased, and the peak position of 3D fluorescence scan shifted to shorter wavelength.     

Estimation of colored dissolved organic matter and salinity fields in case 2 waters using SeaWiFS: Examples from Florida Bay and Florida Shelf

Estimates of water quality variables such as chlorophylla concentration (Chl), colored dissolved organic matter (CDOM), or salinity from satellite sensors are of great interest to resource managers monitoring coastal regions such as the Florida Bay and the Florida Shelf. However, accurate estimates of these variables using standard ocean color algorithms have been difficult due to the complex nature of the light field in these environments. In this study, we process SeaWiFS satellite data using two recently developed algorithms; one for atmospheric correction and the other a semianalytic bio-optical algorithm and compare the results with standard SeaWiFS algorithms. Overall, the two algorithms produced more realistic estimates of Chl and CDOM distributions in Florida Shelf and Bay waters. Estimates of surface salinity were obtained from the CDOM absorption field assuming a conservative mixing behavior of these waters. A comparison of SeaWiFS-derived Chl and CDOM absorption with field measurements in the Florida Bay indicated that although well correlated, CDOM was underestimated, while Chl was overestimated. Bottom reflectance appeared to affect these estimates at the shallow central Bay stations during the winter. These results demonstrate the need for new bio-optical algorithms or tuning of the parameters used in the bio-optical algorithm for local conditions encountered in the Bay.     

Metal accumulation in surface salt marsh sediments of the Bay of Fundy,Canada

We measured the amount of arsenic, chromium, copper, lead, nickel, vanadium, and zinc accumulated over a five-year period from 1997 to 2002 in surface sediments of seven salt marshes along the New Brunswick coast of the Bay of Fundy, Canada. Study sites extended from outer to inner Bay, spanning a gradient in tidal range (6–12 m) and mean sediment deposition rate (0.27–1.76 cm yr⁻¹). In each study site, metal concentrations were measured in low and high marsh areas. Concentrations of chromium, nickel, and zinc appear to be within their natural range, while arsenic, lead, and vanadium are enriched in some sites. Calculated sediment metal loadings rates showed variability among marsh sites that closely followed sediment deposition patterns, suggesting sediment deposition rate is the driving factor of short-term metal accumulation in Fundy marshes. The value of salt marshes as a sink for metals may be enhanced by high sedimentation rates.     

Arsenic distribution in the dissolved, colloidal and particulate size fraction of experimental solutions rich in dissolved organic matter and ferric iron

Due to the widespread contamination of groundwater resources with arsenic (As), controls on As mobility have to be identified. In this study we focused on the distribution of As in the dissolved, colloidal and particulate size fraction of experimental solutions rich in ferric iron, dissolved organic matter (DOM) and As(V). Size fractions between <5 kDa and >0.2 μm were separated by filtration and their elemental composition was analyzed. A steady-state particle size distribution with stable element concentration in the different size classes was attained within 24 h. The presence of DOM partly inhibited the formation of large Fe-(oxy)hydroxide aggregates, thus stabilized Fe in complexed and colloidal form, when initially adjusted molar Fe/C ratios in solution were <0.1. Dissolved As concentrations and the quantity of As bound to colloids (<0.2 μm) increased in the presence of DOM as well. At intermediate Fe/C ratios of 0.02-0.1, a strong correlation between As and Fe concentration occurred in all size fractions (R² = 0.989). At Fe/C ratios <0.02, As was mainly present in the dissolved size fraction. These observations indicate that As mobility increased in the presence of DOM due to (I) competition between As and organic molecules for sorption sites on Fe particles; and (II) due to a higher amount of As bound to more abundant Fe colloids or complexes <0.2 μm in size. The amount of As contained in the colloidal size fractions also depended strongly on the initial size of the humic substance, which was larger for purified humic acids than for natural river or soil porewater samples. Arsenic in the particle size fraction >0.2 μm additionally decreased in the order of pH 4 ? 6 > 8. The presence of DOM likely increases the mobility of As in iron rich waters undergoing oxidation, a finding that has to be considered in the investigation of organic-rich terrestrial and aquatic environments.     

Composition of particulate organic matter in the southern Chesapeake Bay: Sources and Reactivity

The distribution of two classes of lipid biomarker compounds (fatty acids and sterols) was used in conjunction with several bulk parameters (total suspended solids, chlorophyll a, and particulate carbon and nitrogen concentrations) to examine spatial and temporal variability in the sources of particulate organic matter (POM) important to southern Chesapeake Bay. Based on these geochemical parameters, we found that suspended and sedimentary organic matter in the southern Chesapeake Bay is derived from autochthonous sources including a mixture of fresh and detrital phytoplankton, zooplankton, and bacteria. The dominant factor contributing to temporal variability during our study was phytoplankton productivity. Enrichments in particulate organic carbon, chlorophyll a, total fatty acids, total sterols, and a number of biomarkers specific to phytoplankton sources were found in particles collected from surface (1 m) and deep (1 m above the bottom) portions of the water column at several sites during the spring bloom in March 1996 and during a localized bloom in July 1995. Comparison of sites at the mouths of two tributaries (York and Rappahannock rivers) to southern Chesapeake Bay with two sites located in the bay mainsterm indicates spatial variation in the composition of POM was not significant in this region of the bay. The energetic nature of this region of the Chesapeake Bay most likely contributes to the observed homogeneity. Comparison with biomarker studies conducted in other estuaries suggests the high levels of productivity characteristic of the Chesapeake Bay contribute to high background levels of POM.     

Observations on the association between mercury and organic matter dissolved in natural waters

Dissolved mercury in estuarine waters from the Mississippi Delta and Florida Everglades is associated with dissolved organic matter which has the properties of fulvic matter found in soils. Ultrafiltration of water samples demonstrated that mercury and dissolved organic carbon are selectively enriched in the < 500 molecular size cut-off fraction. A decrease in high molecular weight dissolved organic matter with increasing salinity in the Everglades exerts a partial control on the mercury content of these estuarine waters.     

Terrigenous dissolved organic matter along an estuarine gradient and its flux to the coastal ocean

The contribution of terrigenous organic matter (TOM) to high molecular weight dissolved and particulate organic matter (POM) was examined along the salinity gradient of the Delaware Estuary. Dissolved organic matter (DOM) was fractionated by ultrafiltration into 1–30 kDa (HDOM) and 30 kDa–0.2 μm (VHDOM) nominal molecular weight fractions. Thermochemolysis with tetramethylammonium hydroxide (TMAH) was used to release and quantify lipids and lignin phenols. Stable carbon isotopes, fatty acids and lignin content indicated shifts in sources with terrigenous material in the river and turbid region and a predominantly algal/planktonic signal in the lower estuary and coastal ocean. Thermochemolysis with TMAH released significant amounts of short chain fatty acids (C₉–C₁₃), not seen by traditional alkaline hydrolysis, which appear to be associated with the macromolecular matrix. Lignin phenol distributions in HDOM, VHDOM and particles followed predicted sources with higher concentrations in the river and turbid region of the estuary and lower concentrations in the coastal ocean. TOM comprised 12% of HDOM within the coastal ocean and up to 73% of HDOM within the turbid region of the estuary. In the coastal ocean, TOM from high molecular weight DOM comprised 4% of total DOC. The annual flux of TOM from the Delaware Estuary to the coastal ocean was estimated at 2.0×10¹⁰ g OC year⁻¹ and suggests that temperate estuaries such as Delaware Bay can be significant sources of TOM on a regional scale.