Sediment-air equilibrium partitioning of semi-volatile hydrophobic organic compounds part 2. Saturated vapor pressures, and the effects of sediment moisture content and temperature on the partitioning of polyaromatic hydrocarbons

A gas saturation methodology was used to determine the sediment/air partition coefficient (K(SA)) for phenanthrene and dibenzofuran on a local sediment from the Campus Lake, Baton Rouge. The effects of sediment moisture content, air relative humidity and temperature on K(SA) for phenanthrene were ascertained. The saturated vapor pressures of the compounds were also measured. The sediment moisture content had a striking effect on K(SA); increasing sediment moisture content decreased K(SA). Temperature also had a dramatic effect on K(SA). The variation with temperature was used to evaluate the heats of adsorption on both 'dry' (< 0.8% by mass of water) and 'wet' (> 6% by mass of water) sediments. The heat of adsorption for phenanthrene normalized to unit molecular surface area indicated for the physically adsorbed organic compound was seven times smaller than that for a water molecule. The experimental value of K(SA) was used to test a proposed theoretical model. A good agreement was observed for both phenanthrene and dibenzofuran. The model can be extended to other compounds and sediment types for prediction of air emissions from exposed sediment and dredged materials.     

Levels, fluxes and time trends of persistent organic pollutants in Lake Thun, Switzerland: Combining trace analysis and multimedia modeling

Levels, mass fluxes, and time trends of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) in Lake Thun, a peri-Alpine lake, are investigated. We present measurements of PBDEs and PCBs in air, lake water, lake sediment, and tributary water. These measurements are combined with a multimedia fate model, based on site-specific environmental parameters from the lake catchment. Measured loadings of PBDEs and PCBs in air and tributaries were used to drive the model. The model satisfactorily reproduces PBDE and PCB congener patterns in water and sediment, but it tends to yield concentrations in water below the measurements and concentrations in sediment exceeding the measurements. A sensitivity analysis reveals that partitioning of PBDEs and PCBs between the aqueous dissolved phase and suspended particulate matter in the water column strongly affects the model results, in particular the concentrations in water and sediment. For lower-brominated PBDEs, approximately 70% and 30% of input into the lake stems from atmospheric deposition and from tributaries, respectively. For heavier PBDEs and all PCBs, rivers appear to deliver the major load (64-92%). Waste water effluents are of minor importance. 50-90% of the total input is buried in the permanent sediment. Sediment burial makes PBDEs and PCBs less available for recycling in the environment, and reduces concentrations in the outflowing river. If use of deca-BDE increases in the future, levels in Lake Thun will follow the same trend. If the use and resulting environmental emissions decrease, concentrations in water will rapidly decline, according to our calculations, while sediment levels will decrease at a considerably slower rate.     

Modeling copper partitioning in surface waters

Suspended particulate matter from the surface waters of the Susquehanna, Christina and Brandywine Rivers was collected by tangential flow filtration to study copper partitioning. Copper adsorption increased with an increase of suspended particles and decreased with low pH values or with an increase of dissolved organic matter. Effects of particulate organic matter on copper distribution between suspended particulate and solution phases were studied using modified aluminum oxide. An increase of particulate organic matter enhanced copper adsorption. Copper adsorption per mass of particulate organic carbon was similar for the different sources of suspended particles. A model, based on copper adsorption on particles and complexation with dissolved organic matter, was developed to assess copper partition coefficient as a function of the easily measurable water quality parameters: pH, alkalinity, dissolved organic carbon and particulate organic matter. The partitioning model was calibrated on pH edge data using suspended particles collected from the three rivers. The model was verified using partitioning data as a function of dissolved organic matter. The model adequately describes the system containing natural suspended solids collected from the surface waters.     

Sorption of chlorinated C1- and C2-hydrocarbons and monocyclic aromatic hydrocarbons on sea sediment

The sorption of chlorinated C₁- and C₂-hydrocarbons and monocyclic aromatic hydrocarbons on sea sediment was studied with a miscible displacement technique. Detection was done either by on-line UV-detection or off-line GC-analysis. Equilibrium partitioning coefficients between the salt water phase and the marine sediment were determined for 11 compounds by fitting their breakthrough curves to a local sorption equilibrium model. Based on the obtained partitioning coefficients and on the measurement of the organic carbon content of the sediment, the sorption into the organic carbon fraction was considered. Log K_oc data (K_oc = organic carbon-water partitioning coefficient) were calculated. A linear relationship between the log K_oc values and the log K_ow data (K_ow = octanol-water partitioning coefficient) was found (r = 0.94, n = 11). However, the sorption was lower than expected from the log K_ow data. Finally, the implications of the experimental results for the sorption behaviour of the compounds in the marine environment were evaluated. It was concluded that the sea sediment does not act as an important sink for these anthropogenic compounds.     

On the use of the partitioning approach to derive Environmental Quality Standards (EQS) for persistent organic pollutants (POPs) in sediments: a review of existing data

A review of experimental data has been performed to study the relationships between the concentration in water, pore water and sediments for different families of organic contaminants. The objective was to determine whether it is possible to set EQS for sediments from EQS defined for surface waters in the Daughter Directive of the European Parliament (COM (2006) 397). The analysis of experimental data showed that even though in some specific cases there is a coupling between water column and sediments, this coupling is rather the exception. Therefore it is not recommendable to use water column data to assess the chemical quality status of sediments and it is necessary to measure in both media. At the moment EQS have been defined for the water column and will assess only the compliance with good chemical status of surface waters. Since the sediment toxicity depends on the dissolved pore water concentration, the EQS developed for water could be applied to pore water (interstitial water); hence, there would be no need of developing another set of EQS. The partitioning approach has been proposed as a solution to calculate sediment EQS from water EQS, but the partitioning coefficient strongly depends on sediment characteristics and its use introduces an important uncertainty in the definition of sediment EQS. Therefore, the direct measurement of pore water concentration is regarded as a better option.     

A field studies and modeling approach to develop organochlorine pesticide and PCB total maximum daily load calculations: Case study for Echo Park Lake, Los Angeles, CA

Echo Park Lake is a small lake in Los Angeles, CA listed on the USA Clean Water Act Section 303(d) list of impaired water bodies for elevated levels of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in fish tissue. A lake water and sediment sampling program was completed to support the development of total maximum daily loads (TMDL) to address the lake impairment. The field data indicated quantifiable levels of OCPs and PCBs in the sediments, but lake water data were all below detection levels. The field sediment data obtained may explain the contaminant levels in fish tissue using appropriate sediment-water partitioning coefficients and bioaccumulation factors. A partition-equilibrium fugacity model of the whole lake system was used to interpret the field data and indicated that half of the total mass of the pollutants in the system are in the sediments and the other half is in soil; therefore, soil erosion could be a significant pollutant transport mode into the lake. Modeling also indicated that developing and quantifying the TMDL depends significantly on the analytical detection level for the pollutants in field samples and on the choice of octanol-water partitioning coefficient and bioaccumulation factors for the model.     

Cadmium adsorption by sediment in a turbulence tank.

The mechanism sediment motion that affects cadmium (Cd) adsorption on sediment particles was studied in a turbulence tank in the presence (and absence) of bed mud. The experimental results were verified by a mathematical model for heavy metal transport-transformation developed for the turbulence tank. The mathematical model includes the equations of water flow, sediment motion, heavy metal transport-transformation, heavy-metal reaction kinematics and equations for prescribing the initial conditions and boundary conditions for the experiment. The model conforms the transport-transformation of heavy-metal pollutants in surface waters to following the law of convective-diffusive of common tracers and the characteristics of fate and transport of sediment motion. Variations of dissolved Cd concentrations and suspended particulate Cd concentrations with time and in the water column were measured and computed. The experimental measurements correspond with the computed results. Both the experimental measurements and computed results show that it takes about 6 h to reach equilibrium condition for cadmium adsorption by sediment particles. This is different from the result obtained from experiments conducted in continuously stirred tank reactors (or batch reactors) in which adsorption equilibrium can be achieved in about 20 min. Determination of the model parameters for sediment adsorption-desorption of metals in the tank is discussed. The experimental and computed results obtained in this study are useful to solve practical engineering problems in surface waters.     

Transport of 14C-labelled PCB compounds from sediment to water and from water to air in laboratory model systems

Tetra-, hexa- and octachlorobiphenyls were added to aquatic model systems composed of undisturbed sediment cores with an overlying water phase. Using impactor plates transport of the compounds from sediment to air was observed. About one per cent of the sediment-bound PCBs recovered in the systems left the water by jet drops from bursting bubbles. The transport of PCBs from the sediment to the air was nearly constant over time, with a transport rate of 0.62 μg · dm^?2 week^?1 for tetrachlorobiphenyl. Tetrachlorobiphenyl was mobile in systems with and without macroinvertebrates and in those fixed with HgCl₂. Hexa- and octachlorobiphenyls were transported from sediment to water mainly by bioturbation processes. The two latter substances had a higher adsorption to particles than tetrachlorobiphenyl. Compared to tetrachlorobiphenyl, more hexa- and octachlorobiphenyls accumulated in chironomids and tubificids.     

Modeled and monitored variation in space and time of PCB-153 concentrations in air, sediment, soil and aquatic biota on a European scale

We evaluated various modeling options for estimating concentrations of PCB-153 in the environment and in biota across Europe, using a nested multimedia fate model coupled with a bioaccumulation model. The most detailed model set up estimates concentrations in air, soil, fresh water sediment and fresh water biota with spatially explicit environmental characteristics and spatially explicit emissions to air and water in the period 1930-2005. Model performance was evaluated with the root mean square error (RMSE_log), based on the difference between estimated and measured concentrations. The RMSE_log was 5.4 for air, 5.6-6.3 for sediment and biota, and 5.5 for soil in the most detailed model scenario. Generally, model estimations tended to underestimate observed values for all compartments, except air. The decline in observed concentrations was also slightly underestimated by the model for the period where measurements were available (1989-2002). Applying a generic model setup with averaged emissions and averaged environmental characteristics, the RMSE_log increased to 21 for air and 49 for sediment. For soil the RMSE_log decreased to 3.5. We found that including spatial variation in emissions was most relevant for all compartments, except soil, while including spatial variation in environmental characteristics was less influential. For improving predictions of concentrations in sediment and aquatic biota, including emissions to water was found to be relevant as well.     

Activated carbon adsorption of trichloroethylene (TCE) vapor stripped from TCE-contaminated water

Ground water contaminated with trichloroethylene (TCE) used in electronic, electric, dry cleaning and the like industries is often treated by air-stripping. In this treatment process, TCE in its vapor form is stripped from ground water by air stream and sometimes emitted into the atmosphere without any additional treatments. Activated carbon adsorption is one of the practical and useful processes for recovering the TCE vapor from the exhaust air stream. However, adsorption of the TCE vapor from the stripping air stream onto activated carbons is not so simple as that from dry air, since in the exhaust air stream the TCE vapor coexists with water vapor with relatively high concentrations. The understanding of the adsorption characteristics of the TCE vapor to be adsorbed on activated carbon in the water vapor-coexisting system is essential for successfully designing and operating the TCE recovery process. In this work, the adsorption equilibrium relations of the TCE vapor adsorption on activated carbons were elucidated as a function of various relative humidity. Activated carbon fibers (ACFs) were used as model activated carbon. The adsorption equilibrium relations were studied by the column adsorption method. The adsorption isotherms of TCE vapor adsorbed on sample ACFs were successfully correlated by the Dubinin-Radushkevich equation for both cases with and without coexistent water vapor. No effects of coexistent water vapor were found on the limiting adsorption volume. However, the adsorption characteristic energy was significantly reduced by the coexistence of water vapor and its reduction was successfully correlated with the equilibrium amount of water vapor adsorbed under the dynamic condition.     

2. The response of a laboratory stream system to PCB exposure: study of periphytic and sediment accumulation patterns

It has been proposed that the accumulation of PCBs by aquatic organisms is a physicochemical process that is governed by the equilibrium partitioning of PCBs between the organisms and the ambient water. This approach focuses primarily on the hydrophobicity of PCBs, while neglecting the biological impacts of PCB accumulation and possible differences in species-specific response. Furthermore, it does not reflect the complex mechanistic aspects of PCB accumulation. Current modeling, while focusing on accumulation via contaminated food, has been for large lake systems and is not appropriate for lower trophic organism interactions. The objective of this research was to evaluate the ecotoxicological fate of PCBs in a laboratory stream system and to determine if species-specific differences in the accumulation and toxic effects of PCBs existed. Bench scale experiments were conducted to determine kinetic and equilibrium parameters measuring algal uptake of PCB, and these results were used to explain the periphytic response to low level PCB exposure in the laboratory stream system. The results revealed that the accumulation rate, accumulation capacity and toxicity of PCBs differed for the species tested. The observation of PCB fate in the laboratory stream system indicated that PCB volatilization, sediment adsorption and periphyton bioaccumulation were the major pathways of PCB fate. The periphytic biolayer was the significant sink for PCB concentration. The accumulation capacity of periphytic biolayer to PCBs was one order of magnitude greater than that of sediments on a TOC basis. Comparison of the experimental data with model predictions illustrates that equilibrium partitioning models are not very accurate for predicting the accumulation of hydrophobic chemicals by low trophic biota.     

Transport of C-labelled PCB compounds from sediment to water and from water to air in laboratory model systems

Tetra-, hexa- and octachlorobiphenyls were added to aquatic model systems composed of undisturbed sediment cores with an overlying water phase. Using impactor plates transport of the compounds from sediment to air was observed. About one per cent of the sediment-bound PCBs recovered in the systems left the water by jet drops from bursting bubbles. The transport of PCBs from the sediment to the air was nearly constant over time, with a transport rate of 0.62 μg · dm⁻² week⁻¹ for tetrachlorobiphenyl. Tetrachlorobiphenyl was mobile in systems with and without macroinvertebrates and in those fixed with HgCl₂. Hexa- and octachlorobiphenyls were transported from sediment to water mainly by bioturbation processes. The two latter substances had a higher adsorption to particles than tetrachlorobiphenyl. Compared to tetrachlorobiphenyl, more hexa- and octachlorobiphenyls accumulated in chironomids and tubificids.     

Characterization of atmospheric concentrations and partitioning of PAHs in the Chicago atmosphere

An intensive sampling program has been undertaken in the absence of precipitation at an urban site, Chicago, to characterize the atmospheric concentration and partitioning of PAHs. Two different sampling programs have been carried out with a large number of samples. Measured ambient concentrations of PAHs were classified as Land and Lake samples based on wind direction and back trajectory calculations. Differences in ambient concentrations of PAHs were observed between Land and Lake samples. The concentrations of PAHs when air originated over the Land were approximately two-four times higher than the concentrations measured when air originated over the Lake. It has been demonstrated that partitioning of PAHs shows a consistent difference between samples taken when wind came from off the land rather than off the water. This was most evident by more shallow slopes for Lake samples compared to the slopes for Land samples, when partition coefficient (K(p)) is plotted on a log-log scale vs. the subcooled liquid vapor pressure (P(L)(0)). Experimentally, determined K(p) values were compared with the results obtained using two different models, one based on absorption into aerosol organic matter and the other adsorption onto soot carbon. Experimental K(p) values generally agreed well with the soot+octanol based model predictions.     

A preliminary model for predicting heavy metal contaminant loading from an urban catchment

The toxicity of heavy metals to biota in urban catchments has been regarded as a very important non-point source pollution issue. Numerous studies on heavy metal pollution in urban receiving waters have found that metal transport by surface runoff is closely correlated to the partitioning of the metal forms between dissolved and particulate phases, where sediment plays an important role in the transport process. Sediment cycling on urban streets, metal binding form, and rainfall character in the catchment area are considered to be the key factors for metal transport. A preliminary model is developed based on these considerations. Starting from classical build-up and wash-off processes for the suspended sediment (SS) on the urban impervious surface, the model links the transport of suspended sediment to the transport of metal species. Monitoring data from a small highway catchment were used in the model development. A total of 47 rain events over 1 year were monitored intensively at short time intervals (5-10 min) for hydrological data, rainfall intensity, and stormwater quality. In developing the model, lead was used for the metal load prediction, as it has been a common fuel additive for urban transportation. Agreement between model results and monitoring data indicates that the model can be used in predicting metal load from impervious urban areas, such as streets and roadways, on a long-term basis.     

The influence of salting out on the sorption of neutral organic compounds in estuaries

The relative (unsaturated) solubility and sorption of 2,2′,5,5′-tetrachlorobiphenyl have been studied along an estuarine salinity gradient. The aqueous compound was salted out with increasing salinity and an aqueous salting constant of about 0.002 l g⁻¹ was derived. Sorption of the compound to estuarine particles increased with increasing salinity for a range of particle concentrations, but the magnitude of this effect (sorption salting constants of about 0.005–0.01 l g⁻¹) indicated that salting out of the aqueous phase was not solely responsible. It is suggested that the hydrophobicity of sediment organic matter is enhanced by its interaction with seawater ions through a reduction in the charge of the particle surface and, possibly, modification of the structure of the organic matter. Examination of literature data on the sorption of neutral organic compounds to estuarine sediment indicates a general increase in sorption with increasing salinity which can be empirically defined by a salting equation. Although charge reduction of estuarine particles is a general observation, it is not possible to establish the general significance of this effect (or any other form of salting out of sediment organic matter) on the sorption of organic compounds in estuaries because appropriate site- and compound-specific aqueous salting constants are unavailable.

Increased sorption at high salinities has obvious implications for the disposal and transport of organic chemicals in estuaries. However, the inverse dependency of sediment–water partitioning on particle concentration is likely to be of at least equal significance in macrotidal environments where sediment resuspension occurs. An empirical model, combining the effects of salinity and particle concentration, is proposed for deriving first-order estimates of the partitioning of neutral organic compounds in estuaries.     

Methylmercury production and distribution in aquatic systems.

Mercury methylation and partitioning between sediment, water and fish were studied in river sediment spiked with mercuric chloride at levels of 1, 5 and 10 ppm as Hg. Maximum methylmercury production in the sediment occurred during the first week of incubation, with concentrations reaching 45.5 ng/g (dry wt.). Equilibrium conditions were established 3-4 weeks after the contamination of the sediment with mercury. Methylmercury partitioning between sediment and water yielded methylmercury levels of 25-154 ng/l in the fish aquariums and 0.26 ng/l in the fish-free control after 1 week of incubation. Equilibrium levels were 1.5-5.5 ng/l and 0.53 ng/l, respectively, during the 7th week. Over 50% of the methylmercury in whole water were in soluble form or associated with colloidal particulate < 1 micron. Mercury concentration in fish increased almost exponentially from 30 ppb to an average of 345 ppb within 3 weeks. Mercury uptake rates by fish were in the range of 10-18 ng/g per day during the 2nd and 3rd weeks, high rates occurring in water with methylmercury to total mercury ratios > 0.45. The partition coefficients for total mercury and methylmercury between fish and water (Kf-w) were 5000-7000 and 10,000-22,000, respectively. Large differences were observed in methylmercury production in sediment-water incubation with fish and the fish-free control. Equilibrium methylmercury concentrations in sediment were in the range 15-32 ng/g in the aquariums containing fish and 3-4.5 ng/g in the fish-free control. The significance of fish in mercury methylation in the aquariums still remains to be clarified as fish itself cannot methylate mercury in vivo.     

Uncertainty and variability in risk from trophic transfer of contaminants in dredged sediments.

The risks associated with bioaccumulative contaminants must be considered when evaluating dredged material disposal alternatives. The bioaccumulation of organochlorines and other contaminants by higher trophic level organisms represents one of the most significant sources of uncertainty in risk assessment. Both population variability (e.g. true population heterogeneity in body weight, lipid content, etc.) and uncertainty (e.g. measurement error) in trophic transfer can lead to large errors in predicted risk values for ecological receptors. This paper describes and quantitatively evaluates sources of uncertainty and variability in estimating the risk to an ecological receptor (osprey) from the trophic transfer of polychlorinated biphenyls (PCBs) in sediments from the New York-New Jersey (NY-NJ) Harbor. The distribution of toxicity quotients is obtained using a food chain model for the osprey and specifying distributions for input parameters, which are disaggregated to represent either uncertainty or variability. PCB concentrations in sediment and water are treated as predominantly uncertain, whereas lipid content in fish, feeding preferences, and fish weight are assumed to contribute primarily to population variability in PCB accumulation. The analysis shows that point estimates of reasonable maximum exposure (RME) exceed the uncertainty bounds on the 95th percentile of variability. The analysis also shows that uncertainties in the sediment and water contaminant concentrations contribute more to the range of risk estimates than does the variability in the population exposure parameters. The separation of uncertainty and variability in food chain models can help to support management decisions regarding dredged material disposal by providing a quantitative expression of the confidence in ecological risk estimates. A rationale is provided for the distinction between uncertain and variable parameters based on management goals and data availability.     

Phosphorus adsorption on natural sediments: modeling and effects of pH and sediment composition

The classic Langmuir isotherm equation was modified to describe phosphorus (P) adsorption on P-polluted sediments. The P adsorption characteristics of six sediment samples from Chinese Taihu Lake were studied by short-term isotherm batch experiments and related to sediment composition. The maximum P adsorption capacities (PAC) and P-binding energy constant (k) were obtained by nonlinearly fitting sorption data using the modified Langmuir isotherm model. Native adsorbed exchangeable phosphorus (NAP), the zero equilibrium P concentration value (EPC(0)), and partitioning coefficients (K(p)) were subsequently calculated by corresponding formulae. K(p) and PAC were linearly related to the contents of active Fe and Al in sediments by least squares regression analyses (R(2) approximately 0.9 for both). The effect of pH in a wide range on adsorption process was investigated and H2PO4- was presumed to be the preferential sorption species in overall sorption process. The fact that the amount of P sorbed and zeta potential of sediment particles have no necessary relationship reveals that a strong contribution to the P binding still comes from a ligand-exchange process on the Me-OH(2+) and Me-OH sites rather than electrostatic attraction. In addition, the influence of oxidation-reduction potential (ORP) was investigated and discussed and the dual nature of sediments as a pool or source of P in natural waters was evaluated in site T1-T4.     

Cycling and ecosystem impact of metals in contaminated calcareous dredged sediment-derived soils (Flanders, Belgium)

Significant areas in Flanders, Belgium exhibit moderate contamination with trace metals caused by disposal of contaminated dredged sediments. After disposal, the sediments develop into a soil-like material, on which vegetation is planted or develops spontaneously. Behaviour, cycling and ecosystem impacts of trace metals in calcareous dredged sediment disposal sites in Flanders is reviewed. Although soil physico-chemical properties favour a low metal bioavailability, pore water concentrations can be elevated compared to pore water in uncontaminated soils. While metal leaching is not considered to be of concern, several plants accumulate elevated levels of Cd and Zn in leaves. Also metal levels in soil dwelling organisms and small mammals, particularly Cd, are elevated compared to reference situations. This raises concern for an enhanced transfer of metals to the food chain. Future research should identify biological effects on organisms caused by the contamination. A comprehensive knowledge of metal behaviour in these sites is essential for developing appropriate management options for these sites.