Effects of organic matter heterogeneity on sorption and desorption of organic contaminants by soils and sediments

This review highlights the major progress over the last decade on characterization of geochemically heterogeneous soil/sediment organic matter (SOM) and the impacts of SOM heterogeneity on sorption and desorption of hydrophobic organic contaminants (HOCs) under equilibrium and rate limiting conditions. Sorption and desorption by soils and sediments are fundamental processes controlling fate and transport of less polar and nonpolar organic pollutants in surface aquatic and groundwater systems. Recent studies have shown that soils and sediments exhibit an array of HOC sorption phenomena that are inconsistent with an early partition model based on an assumption of homogeneous gel-like SOM. Increasing data have revealed that isotherm nonlinearity, varied sorption capacity, sorption–desorption hysteresis, and slow rates of sorption and desorption are characteristics for HOC sorption by soils and sediments. These phenomena have been shown to result from different types of condensed SOM that exhibit capacity limiting sorption processes. Recent findings of glass transition phenomena and the nonlinear HOC sorption by humic acids provide a scientific foundation for drawing an analogy between humic acids and synthetic organic polymers that supports a dual mode model for sorption by soils and sediments. Humic acid is glassy or rigid at temperatures lower than its glass transition temperature and exhibits relatively nonlinear sorption isotherms for HOCs. Fractionation and quantification of SOM indicate that soils and sediments contain significant amounts of black carbon and kerogen of different origins. These particulate organic materials have rigid 3-dimensional structures and are often less polar compared to humic substances. Limited studies show that black carbon and kerogen exhibit nonlinear sorption for HOCs and may dominate the overall nonlinear sorption by soils and sediments.     

Organic matter in small mesopores in sediments and soils

The three-way correlation among organic matter concentrations, specific surface area and small mesopores observed for many soils and sediments led to the hypothesis that enclosure within the pores might explain the apparent protection of organic matter by minerals. We test this hypothesis by examining whether the bulk of organic matter resides within small mesopores. Pore volumes as a function of pore width were measured before and after organic matter removal, and the volume differences ascribed to organic matter filling of pores. Minor changes in small mesopore size distributions upon treatments such as centrifugation and muffling indicate the robustness of the mineral matrices that form these pores. We developed an additional method to assess organic matter densities using high-resolution pycnometry, and used these densities to convert pore volumes to organic matter contents. Although smaller mesopores are shown to have sufficient volumes to contain significant fractions of the total organic matter, only small fractions of total organic matter were found to reside in them. These results are consistent with preferential association between organic matter and aluminous clay particle edges, rather than the largely siliceous clay faces that contribute most surface area and form pore walls. While simple enclosure within smaller mesopores cannot, therefore, explain protection, network effects working at larger size scales may account for exclusion of digestive agents and hence organic matter protection.     

The distribution and source of organic matter in reservoir sediments

The bottom sediments of two reservoirs, one with significant river sediment input and one without, were analyzed for organic matter content. Lake Texoma sediments average 1.0% organic carbon, of which 0.26% organic carbon is deposited by the river sediments of the Red and Washita River deltas. In Fort Gibson reservoir, where there is minimal river sediment input, the organic carbon averages 1.2% and is deposited with a strong correlation to water depth (+0.9). There is a significant difference between the C/N ratio of Lake Texoma sediments (11.5) and Fort Gibson sediments (9.6). The higher C/N ratio is suggested to be a result of the larger input of terrestrial plant debris (with a high original C/N ratio) by the rivers draining into Lake Texoma and the relatively high resistance of the lignin material in the plant debris to decomposition in the reservoir sediments.     

Effect of organic amendments on arsenic solubilization in soils during long-term flooded incubation

Rice consumption is considered an important arsenic source for the population in Asian countries. Previous studies showed increase in arsenic solubility in flooded soils and arsenic uptake by rice plants with the application of organic amendments, while contrasting results were also reported. Here, we comprehensively examined the effect of three types of organic amendments on arsenic solubility during long-term flooded soil incubation. The amendments examined were categorized as (1) plant-based composts, (2) cattle manures, and (3) fermented livestock (swine and poultry) droppings. The dissolved arsenic in all soils with fermented livestock dropping was significantly greater than that in control soils at 10 and 39 days after incubation. The soils with two cattle manures also contained significantly greater amounts of dissolved arsenic than control soils at day 39, while the rest of the amendments did not increase arsenic solubility. At day 80, the amount of dissolved arsenic in all soils became comparable. Tukey’s test demonstrated that the relative ratio of dissolved arsenic in soils with fermented livestock droppings to control soils was significantly greater than those with the plant-based composts and cattle manures at days 10 and 39. Furthermore, the solubilizing effect of some organic amendments was mostly explained by promotion of decrease in soil Eh, rather than increase in dissolved organic carbon. Thus, it could be concluded that fermented livestock droppings potentially have a greater risk of solubilizing As than plant-based composts and cattle manures, because of their greater ability for accelerating soil reduction, associated with their higher bio-decomposability.     

Sulfate reduction and the nature of organic matter in estuarine sediments

The reduction of sulfate by sulfate reducing bacteria in the anoxic zone is an extremely important process during early diagenesis of marine sediments. Our data from Great Bay, NH reinforce the proposal that the rate of sulfate reduction is directly proportional to the reactivity of the organic matter or the amount of readily metabolizable organic matter present in the sediment and, hence, the source of the organic material in the anoxic zone. It appears that organic matter rich in marine organic remains is more easily degraded in the anoxic zone and that sulfate reduction rates can vary considerably in an estuarine system where many types of organic material may be deposited.     

Determination of organic carbon in soils and sediments in an automatic method

Our automatic digestion device is applied in determining the quantity of organic carbon in the soils/sediments. Its operation process is simple. The reaction conditions are optimized; the complex pretreatments are automated; and a great number of samples can be analyzed at the same time. Comparison shows that the experiment using the device is safer and easier. The correlation coefficiency is greater than 0.999, indicating a good linear relationship. The relative standard deviations of three different concentrations are less than 5%. Standard addition recoveries of high and low concentration range between 94.7% and 100% and between 91.7% and 105% respectively. Method determination limitation (MDL) of this method meets the practical requirements. The device in this paper supports a compositive SOC determination method. Its advantages include improved time and labor efficiency, and accuracy. The device is widely used in the studies of agricultural science, carbon cycle, climate change and environmental protection.     

A probe for sampling interstitial waters of stream sediments and bog soils

A probe for sampling interstitial waters of stream sediments and bog soils is described. Samples can be obtained within a stratigraphic interval of 2–3 cm, to a depth of 60–80 cm, and with little or no contamination of the samples by sediment or air.     

Land-derived organic matter in surface sediments from the Gulf of Mexico

Lignin oxidation products and ¹³C/¹²C ratios were compared as indicators of land-derived organic matter in surface sediments from the western Gulf of Mexico. Whole sediments were reacted with cupric oxide to yield phenolic oxidation products that indicated the types and relative amounts of the lignins that were present.Measurements of lignin concentration and carbon isotope abundances both indicated a sharp offshore decrease of land-derived organic matter in most areas of the western Gulf. This decrease results primarily from mixing of terrestrial and marine organic matter. The terrestrially derived material in these sediments has a lignin content similar to that of grasses and tree leaves. Flowering plants contribute most of the sedimented lignin compounds. These lignins apparently occur in the form of well-mixed plant fragments that are transported to sea by rivers and deposited primarily on the inner continental shelf.     

Dissolved organic matter in pore water of carbonate sediments from Bermuda

Pore water samples from seven nearshore areas in Bermuda were obtained under in situ conditions and analyzed for dissolved organic carbon, dissolved carbohydrates, dissolved free amino acids and dissolved humic substances. The concentration of dissolved organic carbon is higher than in the overlying nearshore waters indicating significant diagenetic remobilization of carbon in these recently deposited carbonate sediments. Dissolved carbohydrates decrease with depth due to microbial utilization.     

Diagenesis of organic matter in suspended particles and sediments in the Cariaco Trench

Suspended particulate materials and bottom sediments from the Cariaco Trench were analysed for lipid content to investigate the diagenesis of organic matter in an anoxic water column and sediment. Distributions of fatty acids, sterols, and the acyclic isoprenoid hydrocarbons, lycopane and 2,6,10,15,19-pentamethyleicosane, support the hypothesis that alteration of organic matter usually attributed to sedimentary diagenesis occurs in the water column. Typical indicators of diagenetic processes, including preferential loss of unsaturated fatty acids, increased abundances of branched fatty acids, stenol-to-stanol conversion, and abundant acyclic isoprenoids, were observed in the water column across the oxic/anoxic interface in the Cariaco Trench. Lipid distributions in the sediment were remarkably uniform with depth. We conclude that organic material delivered to the sediment has been extensively altered in the water column, but that which is buried is preserved without much additional alteration.     

Effect of organic matter on DOM sorption on lake sediments

The effect of organic matter on the sorption of dissolved organic matter (DOM) on lake sediments is critical to understanding the fate and transport of contaminants at the sediment–water interface in lake ecosystems. Results indicate that DOM sorption on sediment is largely due to ligand exchange between the DOM and hydroxyl groups, and the amount of DOC sorbed is a linear function of added DOC. With increasing organic matter content the sediment has lower binding strength, higher releasing ability for DOM, and the higher amount of DOM sorbed by sediment naturally. There was no clear difference before and after the sediment was treated with H₂O₂, but the constant b implied that after the sediments were treated DOC release was promoted. Organic matter in the sediment tends to impede the sorption of DOC and results in a remarkable decrease in DOC sorption rates.     

Sorptive stabilization of organic matter in soils by hydrous iron oxides

Strong correlations between iron oxides (FeOx) and organic matter (OM) in soils have implied the importance of the former in stabilizing the latter. One mechanism thought to be important in this stabilization is sorption. We tested this possibility by reductively dissolving FeOx in a wide variety of soils and measuring the organic carbon (OC) that was solubilized. The OC dissolved from non-FeOx phases via anion exchange was corrected for by parallel control extractions. The resultant pool, reductively soluble OC, made up a minor amount of total soil OC in all but one of these soils, indicating that simple sorption reactions do not stabilize the bulk of soil OC in most mineral soils. OC:Fe ratios in the extracts from 2/3 of these soils were less than 0.22 (wt/wt), consistent with a sorbed state for this OC and showing that OC sorption by FeOx in these soils is limited by the amount of FeOx. The remaining soils had low pH and high OM concentrations; their higher OC:Fe ratios indicate inclusion of precipitated organo-Fe complexes in the extracts, which are likely only partially extracted by our method. The high volumetric ratios of OM to FeOx found in correlations between them from the literature are inconsistent with a dominant sorption control and point instead to stabilization to other mechanisms such as organo-Fe complexes or ternary associations among FeOx, OM and other minerals.     

Trace metal behaviour in riverine sediments: Role of organic matter and sulfides

Three sediment cores were collected in the Scheldt, Lys and Spiere canals, which drain a highly populated and industrialized area in Western Europe. The speciation and the distribution of trace metals in pore waters and sediment particles were assessed through a combination of computational and experimental techniques. The concentrations of dissolved major and trace elements (anions, cations, sulfides, dissolved organic C, Cd, Co, Fe, Mn, Ni, Pb and Zn) were used to calculate the thermodynamic equilibrium speciation in pore waters and to evaluate the saturation of minerals (Visual Minteq software). A sequential extraction procedure was applied on anoxic sediment particles in order to assess the main host phases of trace elements. Manganese was the most labile metal in pore waters and was mainly associated with carbonates in particles. In contrast, a weak affinity of Cd, Co, Ni, Pb and Zn with carbonates was established because: (1) a systematic under-saturation was noticed in pore waters and (2) less than 10% of these elements were extracted in the exchangeable and carbonate sedimentary fraction. In the studied anoxic sediments, the mobility and the lability of trace metals, apart from Mn, seemed to be controlled through the competition between sulfidic and organic ligands. In particular, the necessity of taking into account organic matter in the modelling of thermodynamic equilibrium was demonstrated for Cd, Ni, Zn and Pb, the latter element exhibiting the strongest affinity with humic substances. Consequently, dissolved organic matter could favour the stabilization of trace metals in the liquid phase. Conversely, sulfide minerals played a key role in the scavenging of trace metals in sediment particles. Finally, similar trace metal lability rankings were obtained for the liquid and solid phases.     

Stable carbon isotope ratio variations of organic matter in Orca Basin sediments

Orca Basin is a highly reducing basin on the slope of the Gulf of Mexico. Stable carbon isotope ratios and total organic carbon percentages were determined for two cores within the basin and one control core outside the basin. The results show that the organic carbon content of the basin cores is consistently 2–3 times greater than that of the control core. The Pleistocene-Holocene boundary, indicated by a break in the δ¹³C depth profile, occurs at a greater sediment depth in the basin cores than in the control core. A small sampling interval has made it possible to detect an unexplained fine structure in the δ¹³C profile not previously observed.     

Mineral phases formed in anoxic sediments by microbial decomposition of organic matter

Microbial decomposition of organic matter in recent sediments of the Landsort Deep—an anoxic basin of the central Baltic Sea—resulted in the formation of a characteristic assemblage of authigenic mineral precipitates of carbonates, sulfides. phosphates and amorphous silica, The dominant crystalline phases are a mixed Mn-carbonate [(Mn_0.85Ca_0.10Mg_0.05)CO₃]. Mn-sulfide [MnS] and Fecarbonate [FeCO₃]. Amorphous Fe-sulfide [FeS]. Mn-phosphate [Mn₃(PO₄)₂] and a mixed Fe-Ca-phosphate [(Fe_0.86Ca_0.14)₃(PO₄)₂] were identified by their chemical compositions only. The variability in composition of these solid phases and their mode of occurrence as a co-existing assemblage constrains the conditions and solution composition from which they precipitated. Estimates of activities for dissolved Fe. Mn. PO₄, CO₃ and S in equilibrium with such an assemblage are close to those found in recent anoxic interstitial water-sediment systems. It is important to have detailed knowledge of the composition and stability conditions of these solid precipitates in order to refine stoichiometric models of interstitial nutrient regeneration in anoxic sediments.     

Bacterial reworking of terrigenous and marine organic matter in estuarine water columns and sediments

Amino acids and the bacterial biomarkers muramic acid and d-amino acids were quantified in the ultrafiltered dissolved, particulate and sedimentary organic matter (UDOM, POM and SOM) of the St. Lawrence system (Canada). The main objectives were to better describe the fate of terrigenous and marine organic matter (OM) in coastal zones and to quantify the bacterial contributions to OM composition and diagenesis. Regardless of their origin, the carbon (C) content of the particles substantially decreased with depth, especially near the water-sediment interface. Major diagenetic transformations of organic nitrogen (N) were revealed and important differences were observed between terrigenous and marine OM. Amino acid contents of particles decreased by 66-93% with depth and accounted for 12-30% of the particulate C losses in marine locations. These percentages were respectively 18-56% and 7-11% in the Saguenay Fjord where terrigenous input is important. A preferential removal of particulate N and amino acids with depth or during transport was measured, but only in marine locations and for N-rich particles. This leads to very low amino acid yields in deep marine POM. However, these yields then increased to a level up to three times higher after deposition on sediments, where SOM showed lower C:N ratios than deep POM. The associated increase of bacterial biomarker yields suggests an active in situ resynthesis of amino acids by benthic bacteria. The N content of the substrate most likely determines whether a preferential degradation or an enrichment of N and amino acid are observed. For N-poor OM, such as terrigenous or deep marine POM, the incorporation of exogenous N by attached bacteria can be measured, while the organic N is preferentially used or degraded in N-rich OM. Compared to the POM from the same water samples, the extracted UDOM was poor in N and amino acids and appeared to be mostly made of altered plant and bacterial fragments. Signs of in situ marine production of UDOM were observed in the most marine location. The POM entering the St. Lawrence Upper Estuary and the Saguenay Fjord appeared made of relatively fresh vascular plant OM mixed with highly altered bacterial debris from soils. In contrast, the POM samples from the more marine sites appeared mostly made of fresh planktonic and bacterial OM, although they were rapidly degraded during sinking. Based on biomarker yields, bacterial OM represented on average ∼20% of bulk C and approximately 40-70% of bulk N in POM and SOM, with the exception of deep marine POM exhibiting approximately two times lower bacterial contributions.     

Diagenesis of vascular plant organic matter components during burial in lake sediments

Diagenetic changes are difficult to distinguish from variations in sources of organic matter to sediments. Organic geochemical comparisons of samples of wood, bark, and needles from a white spruce (Picea glauca) living today and one buried for 10,000 years in lake sediments have been used to identify the effects of diagenesis on vascular plant matter. Important biogeochemical changes are evident in the aged spruce components, even though the cellular structures of the samples are well preserved. Concentrations of total fatty acids dramatically diminish; unsaturated and shorter chainlength components are preferentially lost from the molecular distributions. Concentrations of total alcohols are similar in the modern and 10,000-year-old wood and bark but markedly lowered in the aged needles. Hydrocarbon concentrations and distributions show little diagenetic change in the 10,000-year-old plant materials. Cellulose components in the wood decrease relative to lignin components, although both types of materials remain in high concentration in comparison to other organic components. Aromatization of abietic acid proceeds more rapidly in buried spruce wood than in bark; retene is the dominant polyaromatic hydrocarbon in the aged wood. In contrast to the variety of changes evident in molecular compositions, neither ¹³C values nor C/N ratios differ significantly in the bulk organic matter of modern and aged spruce components.     

Amino acid composition of organic matter associated with carbonate and non-carbonate sediments

Amino acids comprise from 15 to 36% by weight of humic substances from carbonate and non-carbonate sediments. Humic and fulvic acids extracted from carbonate sediments are characterized by an amino acid composition consisting primarily of the acidic amino acids, aspartic and glutamic acid. Humic substances from non-carbonate sediments have a distinctly different amino acid composition consisting primarily of glycine and alanine. Amino acid analyses of various molecular weight fractions of fulvic acids extracted from carbonates show that lower molecular weight fractions have appreciably higher relative abundances of the acidic amino acids compared to higher molecular weight fractions. Based on typical values for carboxyl group content in humic substances, acidic amino acids may be a significant contributor of these functional groups. Carbonate surfaces appear to selectively adsorb aspartic acid-enriched organic matter while non-carbonates do not have this property.     

Sources and transformations of organic matter in surface soils and sediments from a tidal estuary (North Inlet, South Carolina, USA)

Surface soil and sediment samples collected along a forest-brackish marsh-salt marsh transect in a southeastern U.S. estuary were separated into three different fractions (sand, macro-organic matter, and humus) based on size and density. Elemental, stable carbon isotope, and lignin analyses of these samples reveal important contrasts in the quantity, composition, and sources of organic matter, between forest and marsh sites. Elevated nitrogen contents in humus samples suggest nitrogen incorporation during humification is most extensive in forest soils relative to the marsh sites. The lignin compositions of the macro-organic and humus samples reflect the predominant type of vegetation at each site. Lignin phenol ratios indicate that woody and nonwoody litter from, gymnosperm and angiosperms trees (pines and oaks) is the major source of vascular plant-derived organic matter in the forest site and that angiosperm, grasses (Juncus andSpartina) are the major sources of lignin at the marsh sites. The phenol distributions also reveal that oxidative degradation of lignin is most extensive in the forest and brackish marsh zones whereas little lignin decay occurs in the salt marsh samples. In forest soils, most organic matter originates from highly altered forest vegetation while at the brackish marsh site organic matter is a mixture of degradedJuncus materials and microbial/algal remains. Organic matter in the salt marsh appears to be composed of a more complex mixture of sources, including degradedSpartina detritus as well as algal and microbial inputs. Microbial methane oxidation appears to be an important process and a source of¹³C depleted organic carbon in subsurface sediments at this site.