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.     

近岸沉积物再悬浮期间所释放溶解有机物的荧光特征

对采自厦门湾九龙江人海河口的4个沉积物样品进行了室内再悬浮模拟实验,利用荧光激发-发射矩阵光谱(EEMs)研究了再悬浮过程中从沉积物中释放出的有色溶解有机物(CDOM)的荧光特征,同时通过与相应站位沉积物间隙水和底层水的对比分析,探讨了河口近岸海域的沉积物再悬浮作用作为水体中溶解有机物来源之一的可能性.结果表明,对给定站位,CDOM相对荧光强度和溶解有机碳(DOC)含量分布变化非常一致,均为间隙水最高,再悬浮次之,底层水最低;站位之间,底层水和再悬浮水样中CDOM相对荧光强度随盐度的降低而增加,从海端向河端增加的趋势明显.EEMs分析表明,各样品中均存在类腐殖质荧光与类蛋白质荧光团,且模拟实验也表明再悬浮作用可释放类腐殖质与类蛋白质荧光物质到底层水中,表明底质再悬浮将是近岸水体中CDOM的一个重要来源.与相应的底层水相比,间隙水的荧光峰(如峰A/C)的位置发生红移.再悬浮样品中EEMs的荧光团同时表现出相应底层水和间隙水的特征,但是荧光峰(峰A和峰C)的最大激发和发射波长更接近底层水中相应荧光团,与间隙水相比,则发生谱峰位置的蓝移.近海端样品中荧光峰M明显,随着盐度的降低,底层水和再悬浮水样的γ(M/C)值逐渐降低,且海源的峰M由海端向河端逐渐消失,表明峰M属于海洋自生来源.本研究区域DOM的荧光指数在1.61～1.93之间,表明近海端样品DOM主要为生物来源,而近河端样品DOM主要为陆源输入,或者为陆源与生物活动共同作用的结果.     

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.     

Rapid sampling of organic matter in flooded soils and sediments

Estuaries and Coasts - A coring system using a compressed air supply and a sediment shaking procedure using a soil dispersant are described which greatly simplify and shorten the task of...     

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.     

Thermodynamics and organic matter: constraints on neutralization processes in sediments of highly acidic waters

The controls on the internal neutralization of low productivity, highly acidified waters by sulfide accumulation in sediments are yet poorly understood. It is demonstrated that the neutralization process is constrained by organic matter quality and thermodynamic effects which control the relative rates of SO₄ and Fe reduction, and the fate of the reduced Fe and S in the sediments. The investigated sediments were rich in dissolved Fe(II) (0.005–12 mmol l⁻¹) and SO₄ (1.3–22 mmol l⁻¹). The pH ranged from 3.0 to 6.8. Contents of reduced inorganic S (0.1–9.5%), molar C/N ratios of the organic matter (12–80) and metabolic turnover rates (1–110 μeq cm⁻³ a⁻¹) varied strongly. Substantial amounts of Fe sulfides were only found at a simultaneous partial thermodynamic and solubility equilibrium of the involved biogeochemical processes. Sulfide oxidation was apparently inhibited, and SO₄ and Fe reduction coexisted. In this type of sediment increases in C availability cause enhanced neutralization rates. In the absence of a partial equilibrium, the sediments were in a sulfide oxidizing and Fe reducing state, and did not accumulate Fe sulfides. The latter type of sediment will increase neutralization rates in response to decreasing deposition of reactive Fe oxides but not necessarily in response to increases in lake productivity by e.g. fertilization measures.     

Partial chemical characterization of estuarine dissolved organic matter

Activated charcoal chromatography was used to isolate dissolved organic matter from a series of water samples collected in Narragansett Bay, Rhode Island, during 1975–1976. The range of dissolved organic carbon values in the samples was 1.46–3.75 mg OC/1. A relatively constant amount of organic carbon was isolated giving overall recoveries of 23 to 63% (mean of 45%). The isolated organic matter was characterized by spectrophotometric measurements, stable carbon isotope determinations, and copper solubilizing capacities. In general, the isolated material displayed considerable constancy in terms of the parameters measured. However, several chemical variations were detected that were probably related to the introduction of organic matter from diatom blooms and terrigenous runoff.     

Effects of estuarine organic matter biogeochemistry on the bioaccumulation of PAHs by two epibenthic species

Polycyclic aromatic hydrocarbon (PAH) biota-sediment accumulation factors (BSAF) were quantified in sediments from two sites in southeastern Louisiana in a 14 d microcosm study usingPalaemonetes pugio, andRangia cuneata and two radiolabeled PAHs, phenanthrene and benzo[a]pyrene (b[a]p). For both PAHs studied, mean BSAFs were significantly higher (p<0.0001) in both organisms in sediments from Bayou Trepagnier, (BSAF=0.628 g OC g TLE⁻¹), a brackish swamp, compared to Pass Fourchon (0.065 g OC g TLE⁻¹), a coastal salt marsh. In order to explain observed patterns in BSAFs, organic carbon-normalized PAH distribution coefficients between the sediment and freely dissolved phases (K_OC)_OBS were determined as well as the various geochemical variables of particulate and dissolved organic matter (POM and DOM, respectively). These included analyses of particle surface area, total organic carbon (TOC), carbon to nitrogen ratios (C∶N), and dissolved organic carbon (DOC). Bayou Trepagnier was higher in surface area, TOC, C∶N, as well as DOC suggesting that the difference in BSAFs may be attributed to compositional differences in POM and DOM between sites. We can not exclude the possibility that other factors (such as differences in organism behavior resulting from contrasting sediment characteristics) were responsible for BSAFs varying between the two sites. Phenanthrene BSAFs were typically higher than b[a]p BSAFs, suggesting contaminants were limited in their desorption from sediment particles as a function of PAH molecular weight. Mean BSAFs for both PAHs were higher on Day 7 than on Day 14. The reason for this decrease is unclear, but did not appear to be due to organisms becoming increasingly stressed in the microcosms. Visual observations indicated that animals remained feeding while no decreases in organism total lipid levels were detected. The trends in BSAFs between sites and over the time course of this experiment suggest that contaminant bioaccumulation in estuarine systems should not be considered to be an equilibrium process.     

从水体到沉积物:探寻有机质的沉积过程及其意义

自然界中有机质分布广泛、类型多样且性质各异,不论在水体还是在沉积物(岩)中都扮演着重要的角色。因此,探讨各类型有机质聚集和沉积过程的差异性,对深化认识有机质沉积特征和演化规律具有重要的意义。生物体在生长过程中产生了许多有机质,包括生物体自身、生物残体、动物排泄物以及生物分泌的有机分子等,各类型有机质的性质差异极大。由于研究方法的不同,可将海洋中有机质划分为颗粒有机质(particulate organic matter,POM)和溶解有机质(dissolved organic matter,DOM),而DOM又可划分为胶体有机质(colloidal organic matter,COM)和真溶解有机质;从聚合体形式上看,又有海雪和悬浮体等存在形式。进一步分析发现有机质的形态包括生物体、生物残体、排泄物和有机质聚合体等,并且各类型有机质与无机矿物以不同的形式共存。此外,DOM与POM间存在一定的转化关系。这些性质和特征架起了不同类型有机质间聚集和沉积的桥梁。在沉积物(岩)中通过粒度或密度分级分离及孢粉相分析,也发现不同类型的有机质,如生物体、生物残体和无定形等,它们常与特定的无机矿物共生,如无定形多富集在黏粒级颗粒中,而生物体和生物残体多富集在粗颗粒中。进一步溯源发现沉积物(岩)中的各类有机质与生物有机质或海洋中有机质的类型极具相似性,这些特征展现各类型有机质在沉积过程中的差异性。综合有机质的形态、性质以及与矿物共生关系,认为有机质可通过机械沉积、化学沉积和生物沉积等3种不同的方式沉积保存,其中机械沉积的有机质以惰性的生物残体为主,化学沉积的有机质以活性极强的无定形为主,生物沉积有机质以活性较强的微生物和粘附物为主。有机质沉积方式及有机质特征、矿物—有机质间关系和保存条件的差异,决定了有机质的演化命运的不同,进而对有机质生烃以及碳循环产生重要的影响,因而应引起人们的高度关注。     

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.     

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.     

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.     

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.     

Recolonization of estuarine sediments by macroinvertebrates: Does microcosm size matter?

Microcosms containing defaunated, fine estuarine sediments were field deployed to assess the effects of microcosm size on the rate of benthic macroinvertebrate recolonization and resulting community structure. Four sizes of microcosms (square acrylic plastic boxes: 7 cm side^?1, 12 cm side^?1, 20 cm side^?1, and 32 cm side^?1, all 6-cm deep) were deployed in upper Perdido Bay, Florida, and colonized for 6 wk. Absolute mean total number of organisms (TNO) differed (α=0.05) among all sizes, while normalized mean TNO (adjusted to 12 cm side^?1 area) did not. Mean total number of taxa (TNT) was different among sizes: 7 cm side^?1, 12 cm side^?1, and 20 cm side^?1, but not between sizes 20 cm side^?1 and 32 cm side^?1. Seven dominant taxa occurred in all size microcosms. Scaling of physical design features (size of microcosm) affected numbers of taxa in recolonization of fine-grained sediments in our study area, but effects on abundance and dominance were minimal.     

Research on the carbon isotopic composition of organic matter from Lake Chenghai and Caohai Lake sediments

The carbon isotopic composition of organic matter from lake sediments has been extensively used to infer variations in productivity. In this paper, based on the study of the contents and δ13C values of organic matter in different types of lakes, it has been found that δ13C values of organic matter have different responses to lake productivity in different lakes. As to the lakes dominated by aqutic macrophytes such as Lake Caohai, organic matter becomes enriched in 13C with increasing productivity. As to the lakes dominated by aquatic algae such as Lake Chenghai, δ13C values of organic matter decrease with increasing productivity, and the degradation of aquatic algae is the main factor leading to the decrease of δ13C values of organic matter with increasing productivity. Therefore, we should be cautious to use the carbon isotopic composition of organic matter to deduce lake productivity.     

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.     

Spatial and temporal variations in terrestrially-derived organic matter from sediments of the Delaware estuary

Terrestrially-derived organic matter in sediments of the Delaware Estuary originates from riverine transport of soils and fresh litter, sewage and industrial wastes, and marsh export of organic matter. The quantity, composition, and spatial distribution of terrigenous organic matter in sediments was determined by elemental (C and N), lignin, and stable carbon isotope analyses. Sediments in the upper Delaware Estuary had low organic carbon content and high lignin content. In contrast, sediments in the lower Delaware Estuary had high organic carbon content and low lignin content. There was a slight decrease in the proportion of syringyl and cinnamyl phenols relative to vanillyl phenols between the upper estuary and lower estuary. Differences in lignin and stable carbon isotope compositions between sediments of the Delaware Estuary and sediments of the Broadkill River estuary (an adjoining salt-marsh estuary) supported previous observations that marshes do not export substantial quantities of organic matter to estuaries. Additional results suggested that lignin-rich sediments were concentrated in the upper estuary, most likely in the zone of high turbidity. Furthermore, algal material diluted lignin-rich sediments, particularly in the lower estuary. The weaker algal signal in bottom sediments compared to that in suspended particulate matter suggested algal material was decomposed either in the water column or at the sediment-water interface. Physical sorting of sediments prior to deposition was also indicated by observations of compositional differences between the upper and lower estuary bottom sediments. Finally, seasonal variations in primary productivity strongly influenced the relative abundance of terrestrial organic matter. In fall, however, the proportion of lignin was greatest because of a combination of greater inputs of terrestrially-derived organic matter, lower river discharge, and a decrease in algal biomass.     

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.     

Rate of mercury loss from contaminated estuarine sediments

The concentration of mercury in contaminated estuarine sediments of Bellingham Bay, Washington was found to decrease with a half-time of about 1.3 yr after the primary anthropogenic source of mercury was removed. In situ measurements of the mercury flux from sediments, in both dissolved and volatile forms, could not account for this decrease. This result suggests that the removal of mercury is associated with sediment particles transported out of the study area. This decrease was modeled using a steady-state mixing model.Mercury concentrations in anoxic interstitial waters reached 3.5 μg/l, 126 times higher than observed in the overlying seawater. Mercury fluxes from these sediments ranged from 1.2 to 2.8 × 10^?5 ng/cm²/sec, all in a soluble form. In general, higher Hg fluxes were associated with low oxygen or reducing conditions in the overlying seawater. In contrast, no flux was measurable from oxidizing interstitial water having mercury concentrations of 0.01-0.06 μ/l.