Stabilisation of precipitates of pedogenic dissolved organic matter by multivalent cations

Purpose Precipitation of dissolved organic matter (DOM) by multivalent cations is important for biogeochemical cycling of organic carbon. We investigated to which extent cation bridges are involved in DOM precipitation and how cross-links by cations and water molecule bridges (WaMB) stabilise the matrix of precipitated DOM. Materials and methods DOM was precipitated from the aqueous extract of a forest floor layer adding solutions of Ca(NO3)2, Al(NO3)3 and Pb(NO3)2 with different initial metal cation/C (Me/C) ratios. Precipitates were investigated by differential scanning calorimetry before and after ageing to detect cation bridges, WaMB and restructuring of supramolecular structure. Results and discussion Twenty-five to sixty-seven per cent of the dissolved organic carbon was precipitated. The precipitation efficiency of cations increased in the order Ca < Al < Pb, while the cation content of precipitates increased in the order Pb < Ca < Al. The different order and the decrease in the WaMB transition temperature (T*) for Al/C > 3 is explained by additional formation of small AlOOH particles. Thermal analysis indicated WaMB and their disruption at T* of 53–65 °C. Like cation content, T* increased with increasing Me/C ratio and in the order Ca < Pb < Al for low Me/C. This supports the general assumption that cross-linking ability increases in the order Ca < Pb < Al. The low T* for high initial Me/C suggests less stable and less cross-linked precipitates than for low Me/C ratios. Conclusions Our results suggest a very similar thermal behaviour of OM bound in precipitates compared with soil organic matter and confirms the relevance of WaMB in stabilisation of the supramolecular structure of cation-DOM precipitates. Thus, stabilisation of the supramolecular structure of the DOM precipitates is subjected to dynamics in soils.

Influence of sample matrix on the alkaline extraction of Cr(VI) in soils and industrial materials

An accurate and efficient determination of the highly toxic Cr(VI) in solid materials is important to determine the total Cr(VI) inventory of contaminated sites and the Cr(VI) release potential from such sites into the environment. Most commonly, total Cr(VI) is extracted from solid materials following a hot alkaline extraction procedure (US EPA method 3060A) where a complete release of water-extractable and sparingly soluble Cr(VI) phase is achieved. This work presents an evaluation of matrix effects that may occur during the hot alkaline extraction and in the determination of the total Cr(VI) inventory of variably composed contaminated soils and industrial materials (cement, fly ash) and is compared to water-extractable Cr(VI) results. Method validation including multiple extractions and matrix spiking along with chemical and mineralogical characterization showed satisfying results for total Cr(VI) contents for most of the tested materials. However, unreliable results were obtained by applying method 3060A to anoxic soils due to the degradation of organic material and/or reactions with Fe2+-bearing mineral phases. In addition, in certain samples discrepant spike recoveries have to be also attributed to sample heterogeneity. Separation of possible extracted Cr(III) by applying cation-exchange cartridges prior to solution analysis further shows that under the hot alkaline extraction conditions only Cr(VI) is present in solution in measurable amounts, whereas Cr(III) gets precipitated as amorphous Cr(OH)3(am). It is concluded that prior to routine application of method 3060A to a new material type, spiking tests are recommended for the identification of matrix effects. In addition, the mass of extracted solid material should to be well adjusted to the heterogeneity of the Cr(VI) distribution in the material in question.

High-Frequency in Situ Optical Measurements During a Storm Event: Assessing Relationships Between Dissolved Organic Matter, Sediment Concentrations, and Hydrologic Processes

Dissolved organic matter (DOM) dynamics during storm events has received considerable attention in forested watersheds, but the extent to which storms impart rapid changes in DOM concentration and composition in highly disturbed agricultural watersheds remains poorly understood. In this study, we used identical in situ optical sensors for DOM fluorescence (FDOM) with and without filtration to continuously evaluate surface water DOM dynamics in a 415 km(2) agricultural watershed over a 4 week period containing a short-duration rainfall event. Peak turbidity preceded peak discharge by 4 h and increased by over 2 orders of magnitude, while the peak filtered FDOM lagged behind peak turbidity by 15 h. FDOM values reported using the filtered in situ fluorometer increased nearly fourfold and were highly correlated with dissolved organic carbon (DOC) concentrations (r(2) = 0.97), providing a highly resolved proxy for DOC throughout the study period. Discrete optical properties including specific UV absorbance (SUVA(254)), spectral slope (S(290-350)), and fluorescence index (FI) were also strongly correlated with in situ FDOM and indicate a shift toward aromatic, high molecular weight DOM from terrestrially derived sources during the storm. The lag of the peak in FDOM behind peak discharge presumably reflects the draining of watershed soils from natural and agricultural landscapes. Field and experimental evidence showed that unfiltered FDOM measurements underestimated filtered FDOM concentrations by up to similar to 60% at particle concentrations typical of many riverine systems during hydrologic events. Together, laboratory and in situ data provide insights into the timing and magnitude of changes in DOM quantity and quality during storm events in an agricultural watershed, and indicate the need for sample filtration in systems with moderate to high suspended sediment loads.

The Role of Forest Soils in a Northern New England Effluent Management System

The Carrabassett Valley Sanitary District in Carrabassett Valley, Maine has utilized both a forest spray irrigation system and a Snowfluent™ system for the treatment of their wastewater effluent. This study was designed to evaluate potential changes in soil properties after approximately 20 years of treatment in the forested spray irrigation site and three years of treatment in the field Snowfluent™ site. In addition, grass yield and composition were evaluated on the field study sites. After treatment with effluent or Snowfluent™, soils showed an increase in soil exchangeable Ca, Mg, Na, and K, base saturation, and pH. While most constituents were higher in treated soils, available P was lower in treated soils compared to the controls. This difference was attributed to higher rates of P mineralization from soil organic matter due to an irrigation effect of the treatment, depleting available P pools despite the P addition with the treatment. Most of the differences due to treatment were greatest at the surface and diminished with depth. Depth patterns in soil properties mostly reflected the decreasing influence of organic matter and its decomposition products with depth as evidenced by significantly higher total C in the surface compared to lower horizons. There were decreasing concentrations of total N, and exchangeable or extractable Ca, Mg, Na, K, Mn, Zn, and P with depth. In addition, there was decreasing BS with depth, driven primarily by declining exchangeable Ca and Mg. Imgation with Snowfluent™ altered the chemical composition of the grass on the site. All element concentrations were significantly higher in the grass foliage except for Ca. The differences were attributed to the additional nutrients and moisture derived from the Snowfluent™. The use of forest spray imgation and Snowfluent™ as a wastewater treatment strategy appears to work well. The soil and vegetation were able to retain most of the applied nutrients, and do not appear to be moving toward saturation. Vegetation management may be a key tool for managing nutrient accumulation on the grass sites as the system ages.

Soil characteristics and decomposition of organic matter on Anchorage, Signy and Falkland Islands

Antarctic terrestrial ecosystems have poorly developed soils and currently experience one of the greatest rates of climate warming on the globe. We investigated the responsiveness of organic matter decomposition in Maritime Antarctic terrestrial ecosystems to climate change, using two study sites in the Antarctic Peninsula region (Anchorage Island, 67°S; Signy Island, 61°S), and contrasted the responses found with those at the cool temperate Falkland Islands (52°S). Our approach consisted of two complementary methods: (1) Laboratory measurements of decomposition at different temperatures (2, 6 and 10 °C) of plant material and soil organic matter from all three locations. (2) Field measurements at all three locations on the decomposition of soil organic matter, plant material and cellulose, both under natural conditions and under experimental warming (about 0.8 °C) achieved using open top chambers. Higher temperatures led to higher organic matter breakdown in the laboratory studies, indicating that decomposition in Maritime Antarctic terrestrial ecosystems is likely to increase with increasing soil temperatures. However, both laboratory and field studies showed that decomposition was more strongly influenced by local substratum characteristics (especially soil N availability) and plant functional type composition than by large-scale temperature differences. The very small responsiveness of organic matter decomposition in the field (experimental temperature increase <1 °C) compared with the laboratory (experimental increases of 4 or 8 °C) shows that substantial warming is required before significant effects can be detected.

(Table 1) Cation exchange capacity and other characteristics of soils common in Lower Saxony, Germany

The chemical and biochemical processes associated with the filtration of rainwater through soils, a step in groundwater recharge, were investigated. Under simulated climatic conditions in the laboratory, undisturbed soil columns of partly loamy sands, sandy soils and loess were run as lysimeters. A series of extraction procedures was carried out to determine solid matter in unaltered rock materials and in soil horizons. Drainage water and moisture movement in the columns were analysed and traced respectively. The behaviour of soluble humic substance was investigated by percolation and suspension experiments. The development of seepage-water in the unsaturated zone is closely associated with the soil genetic processes. Determining autonomous chemical and physical parameters are mineral composition and grain size distribution in the original unconsolidated host rock and prevailing climatic conditions. They influence biological activity and transport of solids, dissolved matter and gases in the unsaturated zone. Humic substances, either as amorphous solid matter or as soluble humic acids play a part in diverse sorption, solution and precipitation processes.

Diatoms, total organic carbon, and total nitrogen of sediment core Dethlingen, Germany

To provide insights into the long-term evolution of aquatic ecosystems without human interference, we here evaluate a decadal- to centennial-scale-resolution diatom record spanning about 12 ka of the Holsteinian interglacial (Marine Isotope Stage 11c). Using a partially varved sediment core from the Dethlingen palaeolake (northern Germany), which has previously been studied for palynological and microfacies signals, we document the co-evolution of the aquatic and surrounding terrestrial environment. The diatom record is dominated by the genera Stephanodiscus, Aulacoseira, Ulnaria and Fragilaria. Based on the diatom assemblages and physical sediment properties, the evolution of the Dethlingen palaeolake can be subdivided into three major phases. During the oldest phase (lasting ~1900 varve years), the lake was ~10-15 m deep and characterized by anoxic bottom-water conditions and a high nutrient content. The following ~5600 years exhibited water depths >20 m, maximum diatom and Pediastrum productivity, and a peak in allochtonous nutrient input. During this phase, water-column mixing became more vigorous, resulting in a breakdown of anoxia. The youngest lake phase (~4000-5000 years) was characterized by decreasing water depth, turbulent water conditions and decreased nutrient loading. Based on our palaeolimnological data, we conclude that the evolution of the Dethlingen palaeolake during the Holsteinian interglacial responded closely to (i) changes within the catchment area (as documented by vegetation and sedimentation) related to the transition from closed forests growing on nutrient-rich soils (mesocratic forest phase) to open forests developing on poor soils (oligocratic forest phase), and (ii) short-term climate variability as reflected in centennial-scale climate perturbations.

Heavy metal concentrations in soils, vegetation, earthworms and wood mice from Heteren and Plateaux, The Netherlands

Effects of soil properties on the accumulation of metals to wood mice (Apodemus sylvaticus) were evaluated at two sites with different pH and organic matter content of the soil. pH and organic matter content significantly affected accumulation of Cd, Cu, Pb and Zn in earthworms and vegetation. For Cd, Cu and Zn these effects propagated through the food web to the wood mouse. Soil-to-kidney ratios differed between sites: Cd: 0.15 versus 3.52, Cu: 0.37 versus 1.30 and Zn: 0.33-0.83. This was confirmed in model calculations for Cd and Zn. Results indicate that total soil concentrations may be unsuitable indicators for risks that metals pose to wildlife. Furthermore, environmental managers may, unintentionally, change soil properties while taking specific environmental measures. In this way they may affect risks of metals to wildlife, even without changes in total soil concentrations.

X-ray fluorescence scanning of discrete samples on the Schwalbenberg II loess-paleosol sequence, raw data, magnetic susceptibility, organic carbon and U-ratio as grainsize index

The Schwalbenberg II loess-paleosol sequence (LPS) denotes a key site for Marine Isotope Stage (MIS 3) in Western Europe owing to eight succeeding cambisols, which primarily constitute the Ahrgau Subformation. Therefore, this LPS qualifies as a test candidate for the potential of temporal high-resolution geochemical data obtained X-ray fluorescence (XRF) scanning of discrete samplesproviding a fast and non-destructive tool for determining the element composition. The geochemical data is first contextualized to existing proxy data such as magnetic susceptibility (MS) and organic carbon (Corg) and then aggregated to element log ratios characteristic for weathering intensity [LOG (Ca/Sr), LOG (Rb/Sr), LOG (Ba/Sr), LOG (Rb/K)] and dust provenance [LOG (Ti/Zr), LOG (Ti/Al), LOG (Si/Al)]. Generally, an interpretation of rock magnetic particles is challenged in western Europe, where not only magnetic enhancement but also depletion plays a role. Our data indicates leaching and top-soil erosion induced MS depletion at the Schwalbenberg II LPS. Besides weathering, LOG (Ca/Sr) is susceptible for secondary calcification. Thus, also LOG (Rb/Sr) and LOG (Ba/Sr) are shown to be influenced by calcification dynamics. Consequently, LOG (Rb/K) seems to be the most suitable weathering index identifying the Sinzig Soils S1 and S2 as the most pronounced paleosols for this site. Sinzig Soil S3 is enclosed by gelic gleysols and in contrast to S1 and S2 only initially weathered pointing to colder climate conditions. Also the Remagen Soils are characterized by subtle to moderate positive excursions in the weathering indices. Comparing the Schwalbenberg II LPS with the nearby Eifel Lake Sediment Archive (ELSA) and other more distant German, Austrian and Czech LPS while discussing time and climate as limiting factors for pedogenesis, we suggest that the lithologically determined paleosols are in-situ soil formations. The provenance indices document a Zr-enrichment at the transition from the Ahrgau to the Hesbaye Subformation. This is explained by a conceptual model incorporating multiple sediment recycling and sorting effects in eolian and fluvial domains.

Analysis of soils from King George Island and Casey station, Antarctica

A comparative study was carried out on soils of the maritime (Arctowski, King George Island) and the continental (Casey, Wilkes Land) Antarctic. Soil sampIes are described for surface layers (0-10 cm) by their in situ temperature profiles as well as by field and laboratory analyses of grain sizes, pH and nutrient contents. Active cryoturbation is a main factor of mixing processes in surfaces with high silt and clay content. In both regions processes of podzolisation were recognized. Microclimatic conditions show the importance of small scale processes which are of special importance for freeze-thaw cycles. The distribution of nutrients and other inorganic components is rather homogeneous in regosols and leptosols. But in soils with organic top layers by lichen and moss cushions (crusts) accumulation occurs as well as displacement of metal ions into deeper layers (>10 cm). Histosols show patterns of brown soils. Special attention is given to the origin of nitrogen compounts and the different ways of import of other components (e.g. chloride) into the Antarctic system are discussed.

Mineral and organic geochemistry from Lake Anterne sediments (North French Alps)

A high-resolution sedimentological and geochemical study was performed on a 20 m long core from the alpine Lake Anterne (2063 m a.s.l., NW French Alps) spanning the last 10 ka. Sedimentation is mainly of minerogenic origin. The organic matter quantity (TOC%) as well as its quality (hydrogen (HI) and oxygen (OI) indices) both indicate the progressive onset and subsequent stabilization of vegetation cover in the catchment from 9950 to 5550 cal. BP. During this phase, the pedogenic process of carbonate dissolution is marked by a decrease in the calcium content in the sediment record. Between 7850 and 5550 cal. BP, very low manganese concentrations suggest anoxic conditions in the bottom-water of Lake Anterne. These are caused by a relatively high organic matter (terrestrial and lacustrine) content, a low flood frequency and longer summer stratification triggered by warmer conditions. From 5550 cal. BP, a decrease in TOC, stabilization of HI and higher sedimentation rates together reflect increased erosion rates of leptosols and developed soils, probably due to a colder and wetter climate. Then, three periods of important soil destabilization are marked by an increased frequency and thickness of flood deposits during the Bronze Age and by increases in topsoil erosion relative to leptosols (HI increases) during the late Iron Age/Roman period and the Medieval periods. These periods are also characterized by higher sedimentation rates. According to palynological data, human impact (deforestation and/or pasturing activity) probably triggered these periods of increased soil erosion.

Specific microbial biomarker signatures from Congo fan sediments of ODP site 175-1075, Congo soils, wetland and estuary sediments

Methane (CH4) is a strong greenhouse gas known to have perturbed global climate in the past, especially when released in large quantities over short time periods from continental or marine sources. It is therefore crucial to understand and, if possible, quantify the individual and combined response of these variable methane sources to natural climate variability. However, past changes in the stability of greenhouse gas reservoirs remain uncertain and poorly constrained by geological evidence. Here, we present a record from the Congo fan of a highly specific bacteriohopanepolyol (BHP) biomarker for aerobic methane oxidation (AMO), 35-aminobacteriohopane-30,31,32,33,34-pentol (aminopentol), that identifies discrete periods of increased AMO as far back as 1.2 Ma. Fluctuations in the concentration of aminopentol, and other 35-aminoBHPs, follow a pattern that correlates with late Quaternary glacial-interglacial climate cycles, with highest concentrations during warm periods. We discuss possible sources of aminopentol, and the methane consumed by the precursor methanotrophs, within the context of the Congo River setting, including supply of methane oxidation markers from terrestrial watersheds and/or marine sources (gas hydrate and/or deep subsurface gas reservoir). Compound-specific carbon isotope values of -30 per mil to -40 per mil for BHPs in ODP 1075 and strong similarities between the BHP signature of the core and surface sediments from the Congo estuary and floodplain wetlands from the interior of the Congo River Basin, support a methanotrophic and likely terrigenous origin of the 35-aminoBHPs found in the fan sediments. This new evidence supports a causal connection between marine sediment BHP records of tropical deep sea fans and wetland settings in the feeding river catchments, and thus tropical continental hydrology. Further research is needed to better constrain the different sources and pathways of methane emission. However, this study identifies the large potential of aminoBHPs, in particular aminopentol, to trace and, once better calibrated and understood, quantify past methane sources and fluxes from terrestrial and potentially also marine sources.