Resolving the spatial variability of soil N using fractions of soil organic matter

The spatial variability of soil nitrogen (N) mineralisation has not been extensively studied, which limits our capacity to make N fertiliser recommendations. Even less attention has been paid to the scale-dependence of the variation. The objective of this research was to investigate the scale-dependence of variation of mineral N (MinN, N–NO3− plus N–NH4+) at within-field scales. The study was based on the spatial dependence of the labile fractions of SOM, the key fractions for N mineralisation. Soils were sampled in an unbalanced nested design in a 4-ha arable field to examine the distribution of the variation of SOM at 30, 10, 1, and 0.12 m. Organic matter in free and intra-aggregate light fractions (FLF and IALF) was extracted by physical fractionation. The variation occurred entirely within 0.12 m for FLF and at 10 m for IALF. A subsequent sampling on a 5-m grid was undertaken to link the status of the SOM fractions to MinN, which showed uncorrelated spatial dependence. A uniform application of N fertiliser would be suitable in this case. The failure of SOM fractions to identify any spatial dependence of MinN suggests that other soil variables, or crop indicators, should be tested to see if they can identify different N supply areas within the field for a more efficient and environmentally friendly N management.

Soil mobility of sewage sludge-derived dissolved organic matter, copper, nickel and zinc

A soil (sandy loam) column leaching study aimed to determine the extent of mobility and co-mobility of Cu, Ni, Zn and dissolved organic matter (DOM) released from a surface-application (equivalent to 50 t ds ha(-1)) of anaerobically-digested sewage sludge. Leaching of DOM through It the soil column was found to be almost un-retarded. Decidedly similar behaviour was exhibited by Ni suggesting that it migrated as organic complexes. Whilst Cu was also found to be leached, significant retardation was evident. However, the importance of DOM in promoting the mobility of both Cu and Ni was evidenced by their lack of mobility when added to the soil column as inorganic forms. The presence of DOM did not prevent Zn from becoming completely adsorbed by the soil solid phase. In relation to WHO drinking water guidelines, only Ni concentrations showed potential environmental significance. due to the relatively poor retention of Ni by the sludge solid phase. (C) 2003 Elsevier Ltd. All rights reserved.

Complexation of copper by sewage sludge-derived dissolved organic matter: Effects on soil sorption behaviour and plant uptake

The complexation of Cu by sewage sludge-derived dissolved organic matter (SSDOM) is a process by which the environmental significance of the element may become enhanced due to reduced soil sorption and, hence, increased mobility. The work described in this paper used an ion selective electrode procedure to show that SSDOM complexation of Cu was greatest at intermediate pH values because competition between hydrogen ions and Cu for SSDOM binding sites, and between hydroxyl ions and SSDOM as Cu ligands, was lowest at such values. Batch sorption experiments further showed that the process of Cu complexation by SSDOM provided an explanation for enhanced desorption of Cu from the solid phase of a contaminated, organic matter-rich, clay loam soil, and reduced adsorption of Cu onto the solid phase of a sandy loam soil. Complexation of Cu by SSDOM did not affect uptake of Cu by spring barley plants, when compared to free ionic Cu, in a sand-culture pot experiment. However, it did appear to lead to greater biomass yields of the plant; perhaps indicating that the Cu-SSDOM complex had a lower toxicity towards the plant than the free Cu ion.

Influence of dissolved organic matter on the solubility of heavy metals in sewage-sludge-amended soils

Sewage-sludge-amended soils generally contain elevated levels of organic matter and heavy metals compared to control soils. Because organic matter is known to complex with heavy metals, the solubility behavior of the organic matter in such soils may exert a significant influence on the solubility of the metals. Little is known about such a process. Using batch experiments in which the solubility of organic matter in a heavily sludge-amended soil was artificially manipulated, we show that the solubilities of the heavy metals copper (Cu), nickel (Ni), and lead (Pb) show a strong positive relationship to the solubility of organic matter, particularly at high pH. The results suggest that under field conditions, spatiotemporal variations in the solid-solution partitioning of organic matter may have a bearing on the environmental significance (mobility and bioavailability) of these heavy metals.

Utilizing chromophoric dissolved organic matter measurements to derive export and reactivity of dissolved organic carbon exported to the Arctic Ocean: A case study of the Yukon River, Alaska

The quality and quantity of dissolved organic matter (DOM) exported by Arctic rivers is known to vary with hydrology and this exported material plays a fundamental role in the biogeochemical cycling of carbon at high latitudes. We highlight the potential of optical measurements to examine DOM quality across the hydrograph in Arctic rivers. Furthermore, we establish chromophoric DOM (CDOM) relationships to dissolved organic carbon (DOC) and lignin phenols in the Yukon River and model DOC and lignin loads from CDOM measurements, the former in excellent agreement with long-term DOC monitoring data. Intensive sampling across the historically under-sampled spring flush period highlights the importance of this time for total export of DOC and particularly lignin. Calculated riverine DOC loads to the Arctic Ocean show an increase from previous estimates, especially when new higher discharge data are incorporated. Increased DOC loads indicate decreased residence times for terrigenous DOM in the Arctic Ocean with important implications for the reactivity and export of this material to the Atlantic Ocean.

Influence of particle characteristics and organic matter content on the bioavailability and bioaccumulation of pyrene by clams

Hydrophobic chemicals are known to associate with sediment particles including those from both suspended particulate matter and bottom deposits. The complex and variable composition of natural particles makes it very difficult therefore, to predict the bioavailability of sediment-bound contaminants. To overcome these problems we have previously devised a test system using artificial particles, with or without humic acids, for use as an experimental model of natural sediments. In the present work we have applied this experimental technique to investigate the bioavailability and bioaccumulation of pyrene by the freshwater fingernail clam Sphaerium corneum. The uptake and accumulation of pyrene in clams exposed to the chemical in the presence of a sample of natural sediment was also investigated. According to the results obtained, particle surface properties and organic matter content are the key factors for assessing the bioavailability and bioaccumulation of pyrene by clams. (C) 2002 Elsevier Science Ltd. All rights reserved.

The impact of climate change on the treatability of dissolved organic matter (DOM) in upland water supplies: A UK perspective

Climate change in the UK is expected to cause increases in temperatures, altered precipitation patterns and more frequent and extreme weather events. In this review we discuss climate effects on dissolved organic matter (DOM), how altered DOM and water physico-chemical properties will affect treatment processes and assess the utility of techniques used to remove DOM and monitor water quality. A critical analysis of the literature has been undertaken with a focus on catchment drivers of DOM character, removal of DOM via coagulation and the formation of disinfectant by-products (DBPs). We suggest that: (1) upland catchments recovering from acidification will continue to produce more DOM with a greater hydrophobic fraction as solubility controls decrease; (2) greater seasonality in DOM export is likely in future due to altered precipitation patterns; (3) changes in species diversity and water properties could encourage algal blooms; and (4) that land management and vegetative changes may have significant effects on DOM export and treatability but require further research. Increases in DBPs may occur where catchments have high influence from peatlands or where algal blooms become an issue. To increase resilience to variable DOM quantity and character we suggest that one or more of the following steps are undertaken at the treatment works: a) ‘enhanced coagulation’ optimised for DOM removal; b) switching from aluminium to ferric coagulants and/or incorporating coagulant aids; c) use of magnetic ion-exchange (MIEX) pre-coagulation; and d) activated carbon filtration post-coagulation. Fluorescence and UV absorbance techniques are highlighted as potential methods for low-cost, rapid on-line process optimisation to improve DOM removal and minimise DBPs.

Evaluation of optical techniques for characterising soil organic matter quality in agricultural soils

Soil organic matter (SOM) is one of the main global carbon pools. It is a measure of soil quality as its presence increases carbon sequestration and improves physical and chemical soil properties. The determination and characterisation of humic substances gives essential information of the maturity and stresses of soils as well as of their health. However, the determination of the exact nature and molecular structure of these substances has been proven difficult. Several complex techniques exist to characterise SOM and mineralisation and humification processes. One of the more widely accepted for its accuracy is nuclear magnetic resonance (NMR) spectroscopy. Despite its efficacy, NMR needs significant economic resources, equipment, material and time. Proxy measures like the fluorescence index (FI), cold and hot-water extractable carbon (CWC and HWC) and SUVA-254 have the potential to characterise SOM and, in combination, provide qualitative and quantitative data of SOM and its processes. Spanish and British agricultural cambisols were used to measure SOM quality and determine whether similarities were found between optical techniques and 1H NMR results in these two regions with contrasting climatic conditions. High correlations (p < 0.001) were found between the specific aromatic fraction measured with 1H NMR and SUVA-254 (Rs = 0.95) and HWC (Rs = 0.90), which could be described using a linear model. A high correlation between FI and the aromatics fraction measured with 1H NMR (Rs = −0.976) was also observed. In view of our results, optical measures have a potential, in combination, to predict the aromatic fraction of SOM without the need of expensive and time consuming techniques.

Modeling the photo-oxidation of dissolved organic matter by ultraviolet radiation in freshwater lakes: implications for mercury bioavailability

Uncertainties in projected ultraviolet (UV) radiation may lead to future increases in UV irradiation of freshwater lakes. Because dissolved organic carbon (DOC) is the main binding phase for mercury (Hg) in freshwater lakes, an increase in DOC photo-oxidation may affect Hg speciation and bioavailability. We quantified the effect of DOC concentration on the rate of abiotic DOC photo-oxidation for five lakes (DOC = 3.27–12.3 mg L−1) in Kejimkujik National Park, Canada. Samples were irradiated with UV-A or UV-B radiation over a 72-h period. UV-B radiation was found to be 2.36 times more efficient at photo-oxidizing DOC than UV-A, with energy-normalized rates of dissolved inorganic carbon (DIC) production ranging from 3.8 × 10−5 to 1.1 × 10−4 mg L−1 J−1 for UV-A, and from 6.0 × 10−5 to 3.1 × 10−4 mg L−1 J−1 for UV-B. Energy normalized rates of DIC production were positively correlated with DOC concentrations. Diffuse integrated attenuation coefficients were quantified in situ (UV-A Kd = 0.056–0.180 J cm−1; UV-B Kd = 0.015–0.165 J cm−1) and a quantitative depth-integrated model for yearly DIC photo-production in each lake was developed. The model predicts that, UV-A produces between 3.2 and 100 times more DIC (1521–2851 mg m−2 year−1) than UV-B radiation (29.17–746.7 mg m−2 year−1). Future increases in UV radiation may increase DIC production and increase Hg bioavailability in low DOC lakes to a greater extent than in high DOC lakes.

The development of soil organic matter in restored biodiverse Jarrah forests of South-Western Australia as determined by ASE and GCMS

Background, aim and scope Soil organic matter (SOM) is known to increase with time as landscapes recover after a major disturbance; however, little is known about the evolution of the chemistry of SOM in reconstructed ecosystems. In this study, we assessed the development of SOM chemistry in a chronosequence (space for time substitution) of restored Jarrah forest sites in Western Australia. Materials and methods Replicated samples were taken at the surface of the mineral soil as well as deeper in the profile at sites of 1, 3, 6, 9, 12, and 17 years of age. A molecular approach was developed to distinguish and quantify numerous individual compounds in SOM. This used accelerated solvent extraction in conjunction with gas chromatography mass spectrometry. A novel multivariate statistical approach was used to assess changes in accelerated solvent extraction (ASE)-gas chromatography-mass spectrometry (GCMS) spectra. This enabled us to track SOM developmental trajectories with restoration time. Results Results showed total carbon concentrations approached that of native forests soils by 17 years of restoration. Using the relate protocol in PRIMER, we demonstrated an overall linear relationship with site age at both depths, indicating that changes in SOM chemistry were occurring. Conclusions The surface soils were seen to approach native molecular compositions while the deeper soil retained a more stable chemical signature, suggesting litter from the developing diverse plant community has altered SOM near the surface. Our new approach for assessing SOM development, combining ASE-GCMS with illuminating multivariate statistical analysis, holds great promise to more fully develop ASE for the characterisation of SOM.

In situ degradability of dry matter and neutral-detergent fibre of thorn scrubland forage consumed by goats in the semi-arid region of north Mexico

Three goats provided with oesophageal and ruminal cannulae were used to determine variations in dry matter (DM) and neutral-detergent fibre (NDF) degradability of the forage consumed when grazing thorn scrubland in the semi-arid region of north Mexico, during two consecutive dry and wet periods. Ingesta samples were incubated intraruminally, the data were fitted to the exponential equation P = a + b (1-e(-ct)) and statistically analysed using a randomized-block design. Organic matter and crude protein (CP) contents were higher (P < 0.05) in the wet seasons. Values of NDF were similar in dry and wet season of both years whereas higher numerical values of acid-detergent fibre (ADF), lignin and cellulose were registered in the dry seasons. DM and NDF degradabilities after 24 and 48 h of ruminal incubation were higher (P < 0.05) in the wet seasons. Higher values (P < 0.05) in DM and NDF bag losses at zero time (A fraction) were registered in the two wet seasons. The insoluble but fermentable DM and NDF (B fractions) were higher (P < 0.05) in the 1999 wet season and variable in the rest of the studied period. Numerically higher values of DM and NDF c fraction were found in wet periods, whereas DM and NDF potential degradabilities were higher (P < 0.05) in the wet season in 1999 and similar across seasons in 2000. Lowest (P < 0.05) contents of CP in grazed forage, DM and NDF degradabilities after 48 h of ruminal incubation, and A, and B, and c fractions were observed in the dry seasons. Thus, these results may be related to both the lower feeding value of forage consumed by the animals and lower performance of livestock during this period. Then, the DM and NDF degradability after 48 h, together with the insoluble but fermentable matter and the c fraction permit the nutritive value of the forage consumed by grazing goats to be accurately described.

Elevated atmospheric CO2 changes phosphorus fractions in soils under a short rotation poplar plantation (EuroFACE)

Future high levels of atmospheric carbon dioxide (CO2) may increase biomass production of terrestrial plants and hence plant requirements for soil mineral nutrients to sustain a greater biomass production. Phosphorus (P), an element essential for plant growth, is found in soils both in inorganic and in organic forms. In this work, three genotypes of Populus were grown under ambient and elevated atmospheric CO2 concentrations (FACE) for 5 years. An N fertilisation treatment was added in years 4 and 5 after planting. Using a fractionation scheme, total P was sequentially extracted using H2O, NaOH, HCl and HNO3, and P determined as both molybdate (Mo) reactive and total P. Molybdate-reactive P is defined as mainly inorganic but also some labile organic P which is determined by Vanado-molybdophosphoric acid colorimetric methods. Organic P was also measured to assess all plant available and weatherable P pools. We tested the hypotheses that higher P demand due to increased growth is met by a depletion of easily weatherable soil P pools, and that increased biomass inputs increases the amount of organic P in the soil. The concentration of organic P increased under FACE, but was associated with a decrease in total soil organic matter. The greatest increase in the soil P due to elevated CO2 was found in the HCl-extractable P fraction in the non-fertilised treatment. In the NaOH-extractable fraction the Mo-reactive P increased under FACE, but total P did not differ between ambient and FACE. The increase in both the NaOH- and HCl-extractable fractions was smaller after N addition. The results showed that elevated atmospheric CO2 has a positive effect on soil P availability rather than leading to depletion.We suggest that the increase in the NaOH- and HCl-extractable fractions is biologically driven by organic matter mineralization, weathering and mycorrhizal hyphal turnover.

The effect of organic materials on the mobility and toxicity of metals in contaminated soils

Organic materials such as compost are often proposed as suitable materials for the remediation of contaminated brownfield sites intended for soft end-use. In addition to vitalising the soil, they are also believed to immobilise metals thereby breaking contaminant-receptor pathways and reducing the ecotoxicity of the contaminants. However, some research has demonstrated contradictory effects between composts on metal immobilisation. In the present study, four different composts and a liming product containing organic matter (LimeX70) were tested to examine both their metal retention and toxicity reduction capabilities on three different metal contaminated soils. Leaching tests, a plant growth test with Greek cress (Lepidium sativum), an earthworm (Eisenia fetida) survival and condition test and a bacterial toxicity test using Vibrio fischeri were carried out. The leaching test results showed that spent mushroom compost caused an increase in metal concentration in the leachates, while LimeX70 caused a decrease. The variation in behaviour between different amendments for each soil was high, so a generic conclusion could not be drawn. Toxicity tests showed significant reduction of metal bioavailability and toxicity for Greek cress, earthworms and bacteria. The results also suggest that more research should be undertaken to understand the mechanisms involved in metal complexation using different types of organic matter, in order to optimise the use of organic materials like compost for soil remediation. Crown Copyright (C) 2007 Published by Elsevier Ltd. All rights reserved.

Physico-chemical controls on phosphorus cycling in two lowland streams. Part 2 - The sediment phase

This article investigates the temporal and spatial controls on sediment-phosphorus (P) dynamics in two contrasting sub-catchments of the River Kennet, England. Suspended sediment (collected under representative flow conditions) and size-fractionated bedload (collected weekly for one year) from the Rivers Lambourn and Enborne was analysed for a range of physico-chemical determinands. Total P concentrations were highest in the most mobile fractions of sediment: suspended sediment, fine silt and clay and organic matter (mean concentrations of 1758, 1548 and 1440 mug P g(-1) dry sediment, respectively). Correlation analysis showed significant relationships between total P and total iron (n = 110), total manganese (n = 110), organic matter (n = 110) and specific surface area (n = 28) in the Lambourn (r(2) 0.71, 0.68, 0.62 and 0.52, respectively) and between total P and total iron (n = 110), total manganese (n = 110) and organic matter (n = 110) in the Enborne (r(2) 0.74, 0.85 and 0.68, respectively). These data highlight the importance of metal oxyhydroxide adsorption of P on fine particulates and organic matter. However, high total P concentrations in the granule gravel and coarse sand size fraction during the summer period (mean concentration 228 mug P g(-1) dry sediment) also highlight the role of calcite co-precipitation on P dynamics in the Lambourn. P to cation ratios in Lambourn sediment indicated that fine silt and clay and granule gravel and coarse sand size fractions were potential sources of P release to the water column during specific periods of the summer and autumn. In the Enborne, however, only the granule gravel and coarse sand size fraction had high ratios and a slow, constant release of P was observed. In addition, scanning electron microscopy work confirmed the association of P with calcite in the Lambourn and P with iron on clay particles in the Enborne. The study highlighted the importance of the chemical and physical properties of the sediment in influencing the mechanisms controlling P storage and release within river channels. (C) 2004 Elsevier B.V. All rights reserved.