Environmental bioavailability of hydrophobic organochlorines in sediments—A review

A number of hydrophobic organochlorines, such as hexachlorobenzene and polychlorinated dibenzo‐p‐dioxins/dibenzofurans (PCDD/Fs), have been reported to be persistent and bioaccumulative; however, their availability to biota appear to be limited due to strong sorption to soil/sediment and sequestration with age. Studies to date have shown that the bioavailability of hydrophobic organic chemicals (HOCs) in sediments is highly variable, depending not only on a chemical's lipophicity (K_ow), but also molecular steric conformation and sediment characteristics. A subdomain of sediment organic carbon, so‐called black carbon (BC), which has much higher affinity to planar HOCs than amorphous organic carbon, has been found to be the predominant repository of many HOCs. The sediment/soil‐bound HOCs are composed of a rapid and reversible desorbing labile fraction and a slow‐desorbing, or resistant‐to‐desorbing, nonlabile fraction. The latter can account for up to 98 percent of the total. A number of chemical extraction methods have been under development to measure the actual bioavailable concentrations in soil/sediment and have shown some correlation to the results of bioaccumulation and/or biodegradation tests. To date, most of the published studies on this subject have focused on polynuclear aromatic hydrocarbons (PAHs). This review summarizes the governing processes and the testing methodologies relevant to the environmental bioavailability of hydrophobic organochlorines in soils and sediments. © 2004 Wiley Periodicals, Inc.     

Study of Pollution of the Plitvice Lakes by Water and Sediment Analyses

The process of eutrophication in form of intense plant growth has been observed in some lakes and water streams at the Plitvice Lakes National Park in central Croatia. Here we investigate whether this phenomenon is a consequence of anthropogenic pollution or due to naturally produced organic matter in the lakes. We applied chemical analysis of water at two springs and four lakes (nutrients, dissolved organic carbon (DOC), trace elements) and measurements of surface lake sediments (mineral and organic fraction analyses, trace elements) in four different lakes/five sites. The chemical composition of water does not indicate recent anthropogenic pollution of water because the concentrations of most trace elements are below detection limits. The concentrations of DOC and nutrients are slightly higher in the area of increased eutrophication-plant growth. Also the content of organic matter in the sediment is at the highest level in areas with highest C/N ratio indicating that the organic fraction of this sediment is mainly of terrestrial origin. There is no significant difference among the trace element concentration in the upper segment of all cores, deposited approximately during last 50 years when higher anthropogenic influence is expected due to development and touristic activity, and the lower part of the cores, corresponding to the period approximately 100–200 years before present. The content of trace elements and organic matter in sediments decreases from the uppermost lake downstream. According to our results there is no indication of recent anthropogenic pollution in water and sediment. Higher concentrations of DOC in water as well as phosphorus and some other elements in the lake sediment can be a consequence of input of natural organic matter to the lake water.     

Chemical speciation of carbon in municipal solid waste incinerator residues

Incinerators do not achieve a complete mineralization of organic constituents of municipal solid waste. The solid residues (bottom ash, boiler ash and air pollution control residues) contain carbon which can be determined as total organic carbon (TOC). This work focuses on the TOC composition and its significance to the genesis and diagenesis of the solid residues. An analytical procedure is presented to characterize carbon species by different chemical and microscopic analytical methods. The procedure is based on two steps. In the first step a quantitative classification of TOC into four different carbon species (elemental carbon, water extractable organic carbon, dichloromethane extractable organic carbon and non extractable organic carbon) is performed to obtain a first survey of the TOC composition. Based on this survey a further characterization of individual carbon species is performed. The results of the qualitative and quantitative characterization of carbon species allow to postulate hypotheses on the influence of organic carbon on the long-term behavior of the solid residues.     

Threshold amounts of organic carbon needed to initiate reductive dechlorination in groundwater systems

Aquifer sediment and groundwater chemistry data from 15 Department of Defense facilities located throughout the United States were collected and analyzed with the goal of estimating the amount of natural organic carbon needed to initiate reductive dechlorination in groundwater systems. Aquifer sediments were analyzed for hydroxylamine and NaOH‐extractable organic carbon, yielding a probable underestimate of potentially bioavailable organic carbon (PBOC). Aquifer sediments were also analyzed for total organic carbon (TOC) using an elemental combustion analyzer, yielding a probable overestimate of bioavailable carbon. Concentrations of PBOC correlated linearly with TOC with a slope near one. However, concentrations of PBOC were consistently five to ten times lower than TOC. When mean concentrations of dissolved oxygen observed at each site were plotted versus PBOC, it showed that anoxic conditions were initiated at approximately 200 mg/kg of PBOC. Similarly, the accumulation of reductive dechlorination daughter products relative to parent compounds increased at a PBOC concentration of approximately 200 mg/kg. Concentrations of total hydrolysable amino acids (THAA) in sediments also increased at approximately 200 mg/kg, and bioassays showed that sediment CO₂ production correlated positively with THAA. The results of this study provide an estimate for threshold amounts of bioavailable carbon present in aquifer sediments (approximately 200 mg/kg of PBOC; approximately 1,000 to 2,000 mg/kg of TOC) needed to support reductive dechlorination in groundwater systems. © 2012 Wiley Periodicals, Inc.     

Influence of the Hydrothermal Pre-treatments on the Adsorption Characteristics of Activated Carbons from Woods

The hydrothermal treatments were conducted prior to the carbonization of oak woods and the obtained charcoals were activated using carbon dioxide or water vapor. The hydrothermal treatments brought about the elutions of acid-soluble lignin fractions as well as hemicellulose fractions accompanied with the decomposition of lignin carbohydrate complexes in the cell walls, which lowered not only the carbon yield of charcoal but also the crystal parameters for the carbon crystallites. However, the activated carbons (AC) produced via the hydrothermal pre-treatment showed superior adsorption properties especially for the adsorptions of 2-methylisoborneol and geosmin as compared with the untreated commercial AC. The hydrothermal treatments prior to the carbonization have some potential to increase the fractions of meso-pores effective for the adsorption of globular shaped molecules.     

Assessment of the Ecological Integrity of Traunsee (Austria) Via Analysis of Sediments and Benthic Microbial Communities

Since nearly one hundred years Traunsee experiences the import of tons of liquid and solid waste originating from salt and soda production. Today, the lake exhibits chloride concentrations of up to 170 mg L^-1 and 19% of the lake floor are directly or indirectly influenced by industrial deposits (ID). Based on the comparison of several microbial parameters in unaffected, directly affected and intermediate lake bottom sediments, the ecological integrity of the lake was evaluated. The highly alkaline ID, which were exclusively colonized by microorganisms, harbored a bacterial community reduced by a factor of 10 in abundance and biomass compared to undisturbed sediment areas within the lake. The bacterial community of ID was furthermore characterized by a reduced content of actively respiring cells (INT-formazan reduction), a lower frequency of dividing cells (FDC) and a significantly reduced cell and biomass production. A 80 to 90% reduction in carbon recycling is estimated for the area exclusively covered by ID. Protists, although occasionally absent from the industrial sediments, were in general found to be less sensitive to the contaminant stress. Differences in alkalinity and dissolved organic carbon (DOC) concentrations of sediment porewaters as well as the total organic content and C/N ratios of sediments partly explain the microbial pattern observed at the various sampling sites. Possible consequences of the continuous industrial tailings for the whole lake ecosystem and the validation of the ecological integrity are discussed.     

Study of fine sediments for making lightweight aggregate.

The objective of this study was to investigate the recycling of the fine sediments of Shih-Men Reservoir to manufacture lightweight aggregate. By qualitative and quantitative analysis of the fine sediment and sintered aggregate through soil test, X-ray fluorescence, X-ray diffraction and scanning electron microscopy, a strategy of recycling fine sediment as aggregate for other similar material is proposed. The test results indicate that such fine sediment can be classified as low plastic clay, and clay of such chemical composition is located in the Riley's 'area of bloating'. The particle density of sintered lightweight aggregate decreases when the sintering temperature increases especially above 1200 degrees C due to phase transformation and formation of a vitrified layer on the surface through subsequent dehydration, bloating and collapsing stages. Our findings show that the fine sediment of Shin-Men Reservoir could be a suitable raw material for making expanded lightweight aggregate sintered at 1200 to 1300 degrees C for 10 to 12 min by a programmable furnace and a diffusion process.     

TOC and TOX as indicator parameters for organic contaminants in landfill leachate

The validity of total organic carbon (TOC) or total organic halide (TOX) measurements as surrogate analyses to detect harmful emissions of leachate from landfills is examined. Correlations of analyses from over 1400 random samples obtained between 1984 and 1987 were interpreted. TOC frequently includes high background levels of natural organic materials in the soil and should only be used when reliable measurements of this background exist. TOX provides a qualitative indication of the presence of halogenated pollutants, but is unreliable as a quantitative indicator due to the complexity of leachate chemistry. Neither indicator is capable of detecting small quantities of highly toxic substances.     

Techniques for the evaluation of maturity for composts of industrially contaminated lake sediments

Composting was applied as a bioremediation methodology for the reclamation of dredged sediments of Isnapur, Khazipally and Gandigudem lakes polluted with industrial wastes. The present study is an attempt to elaborate upon organic matter transformations and define the parameters for product maturity adapting chemical and spectroscopic methods during composting. The stability and maturity of sediments were evaluated by assessing parameters like C/N ratio, nitrification index (NH(4)-N/NO(3)-N), water-soluble organic carbon concentration, CO(2) evolution rate, cation exchange capacity and indices such as humification index, E4/E6 ratio, compost mineralization index (ash content/oxidizable carbon), germination index, dehydrogenase, polyphenoloxidase activities and FTIR spectroscopy. The results showed that the changes in the above chemical and biological parameters can be employed as reliable indicators of stability and maturity. The FTIR spectra revealed enrichment in the aromatic groups and a degradation of the aliphatic groups indicating stabilization of the final compost.     

An Overview of Sediment Organic Matter Records of Human Eutrophication in the Laurentian Great Lakes Region

The isotopic and molecular compositions of organic matter buried in lake sediments provide information that helps to reconstruct past environmental conditions and to assess impacts of humans on local ecosystems. This overview of sedimentary records from the North American Great Lakes region describes examples of applications of organic geochemistry to paleolimnological reconstructions. These lakes experienced a succession of human-induced environmental changes that started after completion of the Erie Canal in 1825. Agricultural deforestation in the mid-nineteenth century released soil nutrients that increased algal productivity and caused an associated increase in algal biomarkers in sediment records. Eutrophication that accompanied magnified delivery of municipal nutrients to the lakes in the 1960s and 1970s created excursions to less negative δ¹³C values in sediment organic matter. Increased organic carbon mass accumulation rates mirror the isotopic evidence of eutrophication in the Great Lakes.     

Dynamic Mechanical Properties of Soy Protein Filled Elastomers

Dynamic mechanical properties including temperature effect, stress softening, and Payne effect are studied on the elastomer composites filled with soy protein or carbon black. The comparison of protein composite with well-known carbon black composites provides further insight into the protein composites. The elastomers filled with soy protein aggregates give substantial reinforcement effect when compared with the unfilled elastomers. Approximately 400 times increase in shear elastic modulus was observed when 40% by weight of protein is incorporated into the elastomers. The sample films were cast from the particle dispersion of soy protein isolate and carboxylated styrene–butadiene latex. At the higher temperatures, the shear elastic modulus of soy protein-filled composites does not decrease as much as that of the carbon black-filled composites. The behavior of elastic and loss modulus under the oscillatory strain of different magnitude is similar to that of carbon black reinforced styrene–butadiene rubber. However, carbon black composites show a better recovery behavior after eight cycles of dynamic strain. The reduction of shear elastic modulus with dynamic strain (Payne effect) was compared with Kraus model and the fitting parameter related to the aggregate structure of the soy protein. A reasonable agreement between the theoretical model and experiment was obtained, indicating the Payne effect of the protein-related network structure in the elastomers could also be described by the kinetic agglomeration de-agglomeration mechanism.     

Spatial and Temporal Variations in the Sediment Habitat of Ranunculus spp. in Lowland Chalk Streams – Implications for Ecological Status?

Ranunculus spp. are the dominant plants of lowland chalk stream habitats in England. The spatial variability of sediment characteristics (silt–clay, organic matter, total phosphorus and total nitrogen content) within stands of Ranunculus spp. was investigated in 12 rivers in lowland England. Variability was found to be high and there were no discernible differences between samples taken from within Ranunculus and a limited number of samples from bare substrate. For two of these rivers, comparisons were also made between reaches upstream and downstream of waste water treatment works outfalls in terms of the characteristics of the sediments within Ranunculus stands. In one river a clear increase in sediment nutrient, fine and organic material content was observed downstream but in the other there was no consistent difference. Temporal variability was considered for two rivers in the Frome catchment, Dorset, by analysing the monthly variability in sediment organic matter and silt–clay content beneath Ranunculus stands over an annual cycle of growth and die-back. Whilst a clear pattern of fine and organic material retention consistent with seasonal plant growth patterns was evident at one site, the three sites displayed different temporal patterns. This inconsistency is believed to reflect differences in sediment supply at the three sites.     

Persistence of the De-Icing Additive Benzotriazole at an Abandoned Airport

The environmental fate of many of the additives in the deicing agents used at airports is poorly understood. One and two years after deicing activities ceased, soil and groundwater samples were taken at an abandoned airport. Benzotriazole (BT), a corrosion and flame inhibitor, was found in low concentrations in soils along runways (mean 0.33 mg/kg), at a snow disposal site (0.66 mg/kg), as well as in sediments of a drainage ditch (13 mg/kg). Locally, high BT concentrations were found in the groundwater below the deicing pad, the regeneration plant and the snow disposal site (1.2 to 1100 g/l). Methyl substituted triazoles or tolytriazoles (MeBT) were found in concentrations less than 10% of the BT concentration. Propylene glycol was not detected in soil samples and in only one of the groundwater samples. Microtox tests of the water samples revealed no acute toxic response, however a reduction in nitrification rate was observed (14–43%). The nitrification response could not be related directly to the BT concentration in the samples, although samples with a high BT concentration showed the largest reduction in nitrification rate. BT showed very little sorption in various soil matrices, only peat and compost with a high organic carbon content showed significant sorption. Sorption could be best described using a Freundlich isotherm. These results indicate a high mobility and possibly long persistence of BT in soil and groundwater, which may be attributed to the absence of microbial degradation of BT.     

Quantification of the Erosion Resistance of Undisturbed and Remoulded Cohesive Sediments

Cohesive sediments besides their typical heterogeneity are characterised by structural discontinuity. Particularly, organic consolidated muds are a good example of sediments that consist of vast aggregates, pore water and gaseous products. The texture of a cohesive sediment bed is a result of a number of mutually affecting factors, such as deposition history, mineral and organic composition, kind of biota and oxygen uptake. The presented work attempts to quantify the effect of sediment physical properties and sediments structure on the sediment erosion potential, considering incipient motion and erosion rate. This quantification is made on the basis of comparative testing of both unremoulded and remoulded samples of a river mud. Due attention is paid to sediment handling to preserve the delicate structure of the sediment for the laboratory experiments. Mud with two degrees of consolidation has been examined in a tilting flume under different flow situations. The test results show a typical increase of erosion strength with dry matter concentration of the mud. It has also been found that the structural properties increase the erosion strength for the less consolidated mud. An opposite effect has been recorded for a more consolidated deposit. As a consequence, due to the sediment structure, the original beds differ much less in erosion resistance in relation to the dry mass concentration than their disturbed analogues. Finally, the erosion resistance of the examined mud is compared with data from the literature.     

Effect of Sediment Humic Substances on Sorption of Selected Endocrine Disruptors

Characterizing sorption processes is essential to understand the environmental distribution and toxicity potential of endocrine disruptors in terrestrial and aquatic systems. The sorption behaviors of three endocrine disruptors (bisphenol A (BPA), 17β-estradiol (E2), and 17α-ethynylestradiol (EE2)) on sediments were investigated using batch techniques. Samples were taken from some representative reaches in several major Chinese rivers. More attention has been paid to the effect of sediment organic components on the sorption of BPA, E2, and EE2. The results show that the sediment organic carbon-normalized partition coefficients (K _oc (sed)) for three endocrine disruptors are in the order of EE2 > E2 > BPA, which corresponds to the octanol-water partitioning coefficients (logK _ow) of the compounds. Moreover, the K _oc values for humic substances (K _oc (hs)) are comparable with the K _oc (sed) values and highly dependent on the physico-chemical properties of humic substances in sediments. The UV absorptivity at 272 nm (A ₂₇₂), which suggests the abundance of aromatic rings in humic substance structure, correlates well with the K _oc (hs) values. In addition, the infrared spectra of the humic substances extracted from sediments show four strong bands centered at 3,400 cm⁻¹, 1,625 cm⁻¹, 1,390 cm⁻¹, and 1,025 cm⁻¹. The K _oc (hs) values have a positive linear relation with the peak area ratio for peak at 1,025 cm⁻¹ and a negative linear relation with the peak area ratio between peaks at 1,625 cm⁻¹ and 1,025 cm⁻¹. Hence, the hydrogen bonds play a critical role to the sorption of selected endocrine disruptors.     

Chemical investigations of aquifers affected by pyrite oxidation in the Bitterfeld lignite district

In a large area around the former open-pit lignite mines near Bitterfeld, Germany, groundwater taken from wells was analyzed for the major cations, anions, and trace elements. Quaternary and Tertiary sediments were collected from aquifers exposed on the sides of the pits and from boreholes outside the mines and analyzed for major and trace elements, as well as for carbonate, pyritic sulfur and total organic carbon. The pH and electrical conductivity of the sediments in suspension were measured. Significant differences were determined between the Tertiary sediments of the aquifers that were exposed to atmospheric oxygen during the lowering of the groundwater table and those outside the cone of depression. The greatest differences were found in the pyrite content, the pH values, and the electrical conductivity. In order to map the degree to which the mining of the lignite has affected the quality of the groundwater in the study area, the water samples were divided into six classes on the basis of their sulfate content. The neutralization potential was calculated to estimate the potential for acidification. Prediction of future groundwater quality is based on both (i) the present composition of the groundwater, surface water, and Quaternary and Tertiary aquifer sediments and (ii) the present and future groundwater flow directions. These studies have shown which parameters are important for future groundwater monitoring.     

Investigation of NAPL transport through a model sand cap during ebullition

Nonaqueous‐phase liquid (NAPL) migration from sediments to the surface of water bodies has been reported frequently at sites with sediments contaminated with NAPLs, such as coal tar and creosote. Commonly, transport of NAPL from sediment is facilitated by gas ebullition caused by anaerobic biodegradation of organic matter in the sediment. A remedy often specified for these sites is a sand cap, and sand caps amended with sorbent materials (such as organoclays) are being pilot‐tested. This article discusses a laboratory study to assess the effectiveness of a sand layer for controlling NAPL migration. The study used a test column composed of a Plexiglas tube containing a tar source that was buried beneath a 30‐cm‐thick layer of fine sand. Water was added to the column until 5 cm of standing water covered the sand layer. To simulate ebullition, air was injected into the base of the sand column at approximately 200 mL/min. It was observed that the gas and NAPL migrated primarily through channels and fractures in the sand, and was not filtered through a network of stable pores. Tar migrated through the sand layer in 12 hours and accumulated on the water surface for several hours before losing its buoyancy and settling back down to the sand surface. After ending the tar migration experiment, the test column was frozen to preserve structures in the sand. The study showed that the tar migrated through the simulated sand cap in small (2‐mm) channels only a few sand grains thick. The results of this laboratory work call into question the effectiveness of sand caps for controlling NAPL migration from sediment in the presence of ebullition. © 2009 Wiley Periodicals, Inc.     

Role of iron chemistry in controlling the release of pollutants from resuspended sediments

Aquatic sediments often contain a large number of chemical contaminants that are potential pollutants. It is often presumed that such contaminants are released to the water column during sediment resuspension and, in there, adversely impact aquatic life and other beneficial uses of the water. However, extensive laboratory and field studies of about 100 contaminated sediments from across the United States that specifically addressed this type of release showed that of about 30 common heavy metals, organic compounds, and other potential pollutants, only manganese II and ammonia were released to then remain in the water column after sediment resuspension. These results indicated that the chemistry of aqueous iron controls the availability of many contaminants in resuspended sediment. The formation of ferric hydroxide during sediment suspension into the water column, as a result of the reaction between ferrous iron in the sediments and dissolved oxygen in the water column, leads to rapid scavenging of many contaminants in the Fe(OH)₃ precipitate. The scavenged contaminants are redeposited in the sediments. This article reviews the role of the aqueous chemistry of iron as it relates to controlling the release of potential pollutants from resuspended sediments. © 2005 Wiley Periodicals, Inc.     

The Role of Soil Organic Carbon in Maintaining Surface Elevation in Rapidly Subsiding U.S. Gulf of Mexico Coastal Marshes

Subsidence is a primary factor governing marsh deterioration in Mississippi River deltaic plain coastal marshes. Marsh surface-water level relationships are maintained primarily through soil organic matter accumulation and inorganic sediment input. In this study we examined the role of soil organic matter accumulation in maintaining marsh elevation in a brackish Spartina patens marsh. Measured rates of soil organic accumulation were compared to plant biomass production and soil respiration (carbon dioxide and methane emission) at the study sites. The study demonstrated the importance of plant biomass production to soil organic carbon accumulation in maintaining viable Spartina patens marshes in sediment-deficient coastal environments. The role of Mississippi River freshwater reintroduction in maintaining conditions for organic accretion is discussed.