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.     

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.     

Active capping technology—New approaches for in situ remediation of contaminated sediments

This study evaluated pilot‐scale active caps composed of apatite, organoclay, biopolymers, and sand for the remediation of metal‐contaminated sediments. The active caps were constructed in Steel Creek, at the Savannah River Site near Aiken, South Carolina. Monitoring was conducted for 12 months. Effectiveness of the caps was based on an evaluation of contaminant bioavailability, resistance to erosion, and impacts on benthic organisms. Active caps lowered metal bioavailability in the sediment during the one‐year test period. Biopolymers reduced sediment suspension during cap construction, increased the pool of carbon, and lowered the release of metals. This field validation showed that active caps can effectively treat contaminants by changing their speciation, and that caps can be constructed to include more than one type of amendment to achieve multiple goals. © 2012 Wiley Periodicals, Inc.     

Incorporating Bioavailability Considerations Into the Evaluation of Contaminated Sediment Sites

In March 2011, the Interstate Technology & Regulatory Council (ITRC) Contaminated Sediments Team published a web‐based Technical and Regulatory Guidance on the concepts, processes, and uses of bioavailability in a risk decision‐making framework at a contaminated sediment site. Bioavailability processes, as defined by the National Research Council (NRC; 2003), are the “individual physical, chemical, and biological interactions that determine the exposure of plants and animals to chemicals associated with soils and sediments.” Bioavailability assessment tools aid in the assessment of human and ecological exposure and development of site‐specific remedial objectives. The guidance provides information on the processes that may affect contaminant bioavailability within sediments to understand exposure within ecological and human receptors; supports the development of conceptual site models (CSMs); and describes available tools (biological, chemical, and physical) and models that are used to measure and characterize the fate and transport and potential bioavailability of contaminants. Case studies, referenced throughout the document, demonstrate the practical application of bioavailability measures. The guidance will describe the proper application of traditional and emerging sediment remediation technologies to support the selection of a remedy that is protective of human health and the environment. © 2013 Wiley Periodicals, Inc.     

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.     

Physical impact of waterjet‐based sediment remediation on benthic organisms

Adding activated carbon to sediments has been shown to be an effective means of reducing the bioavailability of certain contaminants. The current state of the practice is to mechanically mix activated carbon to a target concentration of 3 percent at depths of approximately 30 cm using a rotovator or similar construction equipment. Waterjets have been used to cut hard material using a mixture of water and an abrasive. If activated carbon is substituted for the abrasive, waterjets have the potential to use surface injection as a replacement for mechanical mixing during sediment remediation. A perceived benefit of waterjet‐based sediment remediation is that there may be a reduced potential for benthic organism mortality related to amendment delivery. A set of waterjet parameters were identified that have the potential to achieve amendment placement goals, and a series of waterjet tests were conducted to evaluate the potential impact on the benthic community. The tests included mortality testing using a swimming macroinvertebrate and a burrowing invertebrate, benthic artifacts such as shells, and craft foam as a surrogate for living organisms. The results indicated that the immediate survivability was typically greater than 50 percent, and that empirical relationships between two variables (waterjet nozzle diameter and the water column height between the nozzle and the target) and the depth of cut in the foam could be established. Data are not available in the literature for direct comparison of organism survivability immediately after mechanical mixing, but the results of this study provide motivation for the further evaluation of waterjets on the basis of the low observed mortality rates. Future waterjet work may address field‐scale characterization of mixing effectiveness, resuspension potential, technical feasibility, and cost. © 2011 Wiley Periodicals, Inc.     

Bench-scale testing of a novel soil PFAS treatment train for informed remedial planning and decision-making

Bench-scale batch tests were conducted to assess the potential applicability of a combined separation/concentration/destruction treatment train to address soils and sediments impacted by per- and polyfluoroalkyl substances (PFAS) contamination at Schriever Space Force Base with historic aqueous film-forming foam (AFFF). Specifically, a novel treatment train coupling soil washing (for treatment of impacted soil/sediment) with foam fractionation (for treatment of the wash water [WW] generated during soil washing) and electrochemical oxidation (ECO, for treatment of the foam fractionate generated during foam fractionation) was evaluated at the bench scale using site-specific materials. Results presented herein show that the AFFF-impacted sandy soils with low organic content were amenable to treatment via soil washing. However, the removal of hydrophobic PFAS, such as perfluorooctanesulfonic acid (PFOS), from the organic-rich sediments was challenging. Results from batch desorption experiments were within a factor of 2 of those generated by soil washing bench studies, suggesting that simple batch tests can potentially be used to reasonably predict the treatment efficacy of soil washing. Long-chained perfluoroalkyl acids (PFAAs) within the WW were removed more effectively in the foam fractionation studies as compared to short-chain PFAAs. Addition of a surfactant, such as cetrimonium bromide (CTAB), enhanced foaming but only marginally improved the treatment of short-chained PFAAs and in some cases inhibited PFOS removal. ECO reduced PFAS concentrations in the foam fractionate generated during foam fractionation by several orders of magnitude. However, generation of unwanted byproducts may warrant further treatment and/or disposal. Overall, results from this study provide a novel data set highlighting the site-dependent nature of these PFAS remedial technologies and how simple, low-cost bench tests can be reliably leveraged for informed decision-making during PFAS remedial planning.     

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.     

Levels and Characteristics of TOC in Throughfall, Forest Floor Leachate and Soil Solution in Undisturbed Boreal Forest Ecosystems

Total organic carbon (TOC) concentrations and fluxes in throughfall, forest floor leachate, soil solution (15 and 35 cm depths), and groundwater for coniferous forest sites in the boreal zone throughout Finland are described. Eight upland forest stands and one peatland forest stand are included in the study and the samples were collected during 1991–1997. Carbon (C) pools in the living tree biomass and soil compartments are presented, and the hydrophobic/hydrophilic and acidic components of dissolved organic carbon (DOC) in samples collected in autumn 1999 and spring 2000 from two of the sites are compared. Biomass (aboveground and belowground) pools of C averaged 88 Mg ha^-1 and soil (humus layer + 20 cm soil layer) averaged 55 Mg ha^-1. Stand throughfall TOC monthly mean concentrations ranged from 4.0 to 18.6 mg L^-1 and annual fluxes averaged 4.0 g m^-2 yr^-1. TOC concentrations in the water passing through the forest floor and soil decreased with depth. Plot mean concentrations at 35 cm depth values ranged from 4.1 to 21.2 mg L^-1 and fluxes averaged 3.7 g m^-2 yr^-1. Throughfall TOC concentrations were lowest during the winter, snowfall period and highest during the growing season. No monotonic trends in throughfall TOC concentrations over the 1991–1997 period were found. Soil solution TOC concentrations varied considerably, both within and between years. DOC in throughfall, forest floor, and soil solutions and in both autumn and spring seasons was dominated by hydrophobic fractions, particularly acids. Spruce canopies and litter appear to be important sources of soluble organic carbon, particularly acidic and hydrophobic compounds. Further studies on the nature and dynamics of organic carbon fluxing through coniferous, boreal forest ecosystems are needed.     

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.     

Unreliability of co‐occurrence‐based sediment quality guidelines for contaminated sediment evaluations at Superfund/hazardous chemical sites

Many Superfund/hazardous chemical sites include waterbodies whose sediments contain hazardous chemicals. With the need to assess, rank, and remediate contaminated sediments at such sites, as well as in other waterways, regulators seek a simple, quantitative assessment approach that feeds easily into a decision‐making scheme. Numeric, co‐occurrence‐based “sediment quality guidelines” have emerged with the appearance of administrative simplicity. However, the very foundation of the co‐occurrence approach, based on the total concentrations of a chemical(s) in sediment, is technically invalid; its application relies on additional technically invalid presumptions. Use of technically invalid evaluation approaches renders any assessment of the significance of sediment contamination unreliable. This article reviews the technical roots and assumptions of the co‐occurrence‐based SQGs, the fundamental flaws in the rationale behind their development and application, and their misapplication for sediment quality evaluation. It also reviews concepts and approaches for the more reliable evaluation, ranking, and cleanup assessment of contaminated sediments at Superfund sites and elsewhere. © 2005 Wiley Periodicals, Inc.     

Lead Speciation in the Sediments of the Heavily Polluted Western Harbor of Alexandria

The Western Harbor (WH) became under stress in the past decades, following successive increase in population. This study deals with local distribution of total lead and its species in the WH sediments. The lead content was high and there was a relationship between its enrichment and oil dispersed from ships. The lowest total lead value was found in the harbor middle far from direct effects of pollution. A five-step sequential extraction scheme was applied to illustrate the contribution shared by each individual fraction in the total lead concentration in the WH sediments. The exchangeable fraction (F1) was very low. The bound to carbonate fraction (F2), the bound to iron-manganese oxide fraction (F3) and the bound to organic matter—sulfide fraction (F4) ranked fourth, second and third in abundance. Oxygen was the main factor controlling the value of F2. F3 gave a direct relationship with total lead. The high levels of F4 occurred at locations of low salinity and enriched with organic matter. The residual fraction (F5) dominated other lead species, reflecting the sediment composition and the amounts of discharged pollutants.     

Oil-Mineral Aggregate Formation on Oiled Beaches: Natural Attenuation and Sediment Relocation

The significance of oil-mineral aggregate (OMA) formation on the effectiveness of the in situ shoreline treatment options of natural attenuation (natural recovery) and sediment relocation (surf washing) was examined during field trials on two mixed-sediment (sand and pebble) beaches experimentally oiled with IF-30 oil. At both sites, the amount of oil remaining in the experimental plots was dramatically reduced within five days after sediment relocation treatments. Time-series microscopy and image analysis of breaker-zone water samples demonstrate that OMA formation occurred naturally on the oiled beaches at both sites and was accelerated by the sediment relocation procedure. Lower concentrations of OMA in the breaker zone at Site 3 are attributed to the higher wave-energy levels at this site that presumably facilitated more rapid OMA dispersion. The granulometry and mineralogy of beach sediment and of subtidal sediment trap samples indicate that the material settling in nearshore waters originated from the relocated sediment and that a portion of the finer sediment was probably transported out of the study region before settling. Gas chromatography/mass spectrometry analysis demonstrated that a significant fraction of the oil dispersed into nearshore waters and sediments by interaction with mineral fines was biodegraded. The fact that little or no residual oil was found stranded on the shore in areas adjacent to the experimental plots and that only small amounts of oil were found in nearshore subtidal sediments and sediment trap samples suggests that a large fraction of the oil lost from the experimental plots may have been dispersed in the form of relatively buoyant OMA.     

Variations of metal distribution in sewage sludge composting

In the study, the variations of heavy metal distributions (of Cu, Mn, Pb, and Zn) during the sewage sludge composting process were investigated by sequential extraction procedures. The total content of Cu and Zn in the composted mixture increased after the composting process. Mn and Zn were mainly found in mobile fractions (exchangeable fraction (F1), carbonate fraction (F2), and Fe/Mn oxide fraction (F3)). Cu and Pb were strongly associated with the stable fractions (organic matter/sulfides fraction (F4) and residual fraction (F5)). These five metal fractions were used to calculate the metal mobility (bioavailability) in the sewage sludge and composted mixture. The mobility (bioavailability) of Mn, Pb, and Zn (but not Cu) increased during the composting process. The metal mobility in the composted mixture ranked in the following order: Mn>Zn>Pb>Cu.     

Simulation of flow and mercury transport in Upper East Fork Poplar Creek,Oak Ridge,Tennessee

As a result of nuclear processing activities started back in the 1950s, the environment in the vicinity of the Y‐12 National Security Complex (Y‐12 NSC) in Oak Ridge, Tennessee, and surrounding watersheds has been contaminated by nearly 1,000 tons of elementary mercury. To comply with the state and federal surface water quality standards, a significant reduction in mercury concentration to parts‐per‐trillion levels has been proposed. In order to analyze the mercury cycle in the environment and provide forecasting capabilities for the flow and transport of mercury within the Upper East Fork Poplar Creek (UEFPC) watershed, an integrated surface and subsurface flow and transport model has been developed using the hydrodynamic and transport numerical package, MIKE, developed by the Danish Hydraulic Institute. The model has been constructed and calibrated using an extensive collection of historical records (i.e., hydrological data, and mercury concentration measurements in groundwater, soil, and sediment) obtained from the Oak Ridge Environmental Information System database. Daily fluctuations in stream flow, as a result of scattered rainfall, flooding, and flow augmentation, resuspend the contaminated streambed sediments and/or erode the polluted streambank soil and provide a secondary source of mercury to the creek. In order to investigate the significance of sediment‐mercury interactions on the fate and transport of mercury within the UEFPC study domain, simulations were performed for two different cases (i.e., with and without consideration of sediment‐mercury interactions). Computed total suspended solids and mercury concentrations at the integration point of the creek are compared with the corresponding historical records in both cases. As confirmed by the numerical simulations, a substantial portion of the mercury detected in the river is likely in the form of sediment particle–bound mercury (i.e., mercury particulates). © 2012 Wiley Periodicals, Inc.     

Mineralization in a calcareous soil of a sewage sludge composted with different organic residues

Three sewage sludge composts were obtained from mixtures of an aerobic sludge (AS) and three organic wastes differing widely in chemical composition: an extremely biodegradable waste (municipal solid waste, MSW), a plant residue (grape debris) and a residue with a carbon fraction not easily mineralizable (peat residue). The following mixtures were made, the proportions referring to their total organic carbon content: AS-MSW 1/1, AS-GRAPE 3/1 and AS-PEAT 1/1. These mixtures were composted over 3 months in the open air with periodical turning, and were left to mature afterwards for 4 months. Uncomposted mixtures and composted mixtures, before and after maturation, were incubated for 38 days, under laboratory conditions, with a calcareous soil and the CO₂ emission of the samples periodically measured.Uncomposted mixtures emitted much greater quantities of carbon than those composted, whether before or after maturation period. Both at the beginning and at the end of composting, differences were observed between the total amount of carbon emitted by the mixture containing peat waste and the others. However, the quantities of carbon emitted from the three mixtures tended to even out in mature composts, reaching a maximum of 600 mg carbon per 100 g total organic carbon. This shows that, although the mineralization of carbon depends on the nature of the organic waste mixed with the sewage sludge, it tends to even out when the mixtures have undergone composting.     

The potential of foliar treatments for enhanced phytoextraction of heavy metals from contaminated soil

Phytoextraction is the plant‐based removal of inorganic contaminants from the soil by root absorption and subsequent translocation to harvestable plant parts. The efficiency of this technique is limited by the phytoavailability of these contaminants in the soil and the root‐to‐shoot transport. To enhance the phytoextraction efficiency, the use of soil amendments has been widely investigated. Potential risks such as increased ecotoxicological effects and leaching of mobilized contaminants caution against the use of persistent mobilizing agents. The potential use of foliar amendments to enhance mineral absorption and/or translocation offers prospects for complementing or substituting soil amendments for enhanced phytoextraction purposes. This study presents an explorative screening to evaluate the feasibility of this approach. Helianthus annuus giganteus plants were grown in moderately contaminated dredged sediment for ten weeks, with daily foliar treatments from week six onward: (1) distilled water (control), (2) magnesium‐ethylenediaminetetraacetic acid (Mg‐EDTA), (3) diethylenetriaminepentaacetic acid (DTPA), (4) nitrilotriacetic acid (NTA), (5) citric acid, (6) oxalic acid, (7) calcium acetate, (8) ammonium thiocyanate (NH₄SCN), and (9) cystein. Applied doses varied between treatments based on plant tolerance: 15 μmol per plant for cystein, 60 μmol per plant for DTPA and NH₄SCN, 180 μmol per plant for Mg‐EDTA and NTA and 400 μmol per plant for the organic acids. At the end of the experiment, shoot accumulation of cadmium, chromium, copper, iron, manganese, nickel, lead, and zinc was evaluated. © 2004 Wiley Periodicals, Inc.     

Abiotic/biotic degradation and mineralization of N‐nitrosodimethylamine in aquifer sediments

The N‐nitrosodimethylamine (NDMA) degradation rate and mineralization rate were measured in two aquifer sediments that received treatments to create oxic, reducing, and sequential reducing/oxic environments. Chemically reduced sediments rapidly abiotically degraded NDMA to nontoxic dimethylamine to parts per trillion levels, then degraded to further products. NDMA was partially mineralized in reduced sediments (6 to 28 percent) at a slow rate (half‐life 3,460 h) by an unknown abiotic/biotic pathway. In contrast, NDMA was mineralized more rapidly (half‐life 342 h) and to a greater extent (30 to 81 percent) in oxic sediments with propane addition, likely by a propane monooxygenase pathway. NDMA mineralization in sequential reduced sediment followed by oxic sediment treatment did result in slightly more rapid mineralization and a greater mineralization extent relative to reduced systems. These increases were minor, so aerobic NDMA mineralization with oxygen and propane addition was the most viable in situ NDMA mineralization strategy. © 2008 Wiley Periodicals, Inc.