Do aquatic effects or human health end points govern the development of sediment-quality criteria for nonionic organic chemicals ?

The equilibrium partitioning theory may be used to describe the partitioning of nonionic organic chemicals between water, sediment, and aquatic biota. This paradigm was employed to compare the relative magnitudes of organic carbon-normalized sediment-quality criteria that are intended to protect either benthic organisms from the direct toxic effects of sediment-associated chemicals or humans from the indirect health effects posed by the ingestion of contaminated aquatic animals. Comparison of calculated sediment-quality criteria for a variety of hydrophobic chemicals suggests that human health-based end points often result in more restrictive criteria than aquatic effects-based values. Review of published field data indicates that the equilibrium partitioning paradigm may, depending on contaminant class, either over- or underestimate the extent to which sediment-associated contaminations are bioaccumulated. Despite the limitations of adopting this simple theory for criteria development, calculations reveal that regulatory decisions involving sediments contaminated with such chemicals may be dictated by human health concerns if current risk assessment methodologies are applied.     

Sorption kinetics of chlorinated hydrophobic organic chemicals

This is the second of a two-part series describing the sorption kinetics of hydrophobic organic chemicals. Part I “The Use of First-Order Kinetic Multi-Compartment Models” is published in issue 1 of this journal, pp. 21–28. Sorption kinetics of chlorinated benzenes from a natural lake sediment have been investigated in gas-purge desorption experiments. Biphasic desorption curves, with an initial “fast” part and a subsequent “slow” part, were found for all tested chlorobenzenes. From these results first-order sorption uptake and desorption rate constants were calculated with a two-sediment compartment model, which is presented in the first paper. In three sets of experiments the sorption uptake period and sediment/water ratio were varied. Rate constants are not influenced by these experimental conditions, which supports the partitioning concept for the sorption of hydrophobic organic chemicals in sediments.     

Hydrophobic organic compound partitioning from bulk water to the water/air interface

Partitioning of hydrophobic organic compounds to the interface between water and air may significantly affect the distribution and transfer of many xenobiotic chemicals between vapor and aqueous phases. The fluorescent probe, 1-methylperylene, was used to investigate the affinity of hydrophobic compounds for the water–air interface by varying the ratio of interfacial surface area to water volume in a fused-quartz cuvette. We found that the water–air/water interface partitioning coefficient [K_w−awi=1.2 mol cm^-2_awi/(mol ml^-1_w)] for this polycyclic aromatic hydrocarbon (PAH) was quantitatively consistent with partitioning to the same interface but from the airside, recently reported in the literature for less hydrophobic PAHs. Our results demonstrate significant partitioning from bulk water to the water/air interface for a hydrophobicity range relevant to many xenobiotic compounds. Anticipated implications of this process for the environmental chemistry of hydrophobic compounds include retarded gas-phase transport in unsaturated soils, bubble-mediated transport in water, droplet-mediated transport in the atmosphere, and photochemical reactions.     

Influence of contaminated particles on the bioaccumulation of hydrophobic organic micropollutants in fish

The influence of contaminated particles on the bioconcentration of hydrophobic chemicals by fish is dependent on the hydrophobicity of the chemicals. This has been shown for polychlorinated benzenes and biphenyls (ranging over three orders of magnitude in octan-1-ol/water partition coefficient) which are sorbed on very low organic carbon content particles. For chemicals with low to moderate hydrophobicity, the amount of the chemical which is sorbed, relative to the amount which is dissolved, determines the influence that contaminated particles have on the uptake of the chemicals by fish. In this present experiment, for lower chlorinated benzenes and biphenyls, the amount dissolved in water are high compared with the amounts which are present in the sorbed state, and the influence of contaminated particles on their uptake by fish is negligible. For more hydrophobic chemicals, which have lower aqueous solubilities, such as penta and hexachlorobenzene, and tri and tetrachlorobiphenyls, contaminated particles can have a much greater influence on the uptake by fish. If the number of contaminated particles is sufficiently high, the low aqueous solubilities, in combination with relatively high rates of desorption or dissolution, enable the particles to act as a source of the hydrophobic chemicals. For extremely hydrophobic chemicals, the rates of dissolution or desorption determine the rates of uptake of the chemical by the fish. Hence, during relatively short periods of exposure, there is no influence of contaminated particles on the bioaccumulation.     

A flow-through passive dosing system for continuously supplying aqueous solutions of hydrophobic chemicals to bioconcentration and aquatic toxicity tests

A continuous supply of water with defined stable concentrations of hydrophobic chemicals is a requirement in a range of laboratory tests such as the OECD 305 protocol for determining the bioconcentration factor in fish. Satisfying this requirement continues to be a challenge, particularly for hydrophobic chemicals. Here we present a novel solution based on equilibrium passive dosing. It employs a commercially available unit consisting of ∼16 000 polydimethylsiloxane (PDMS) tubes connected to two manifolds. The chemicals are loaded into the unit by repeatedly perfusing it with a methanol solution of the substances that is progressively diluted with water. Thereafter the unit is perfused with water and the chemicals partition from the unit into the water. The system was tested with nine chemicals with log K_OW ranging from 4.1 to 6.3. The aqueous concentrations generated were shown to be largely independent of the water flow rate, and the unit to unit reproducibility was within a factor of ∼2. In continuous flow experiments the aqueous concentrations of most of the study chemicals remained constant over 8 d. A model was assembled that allows prediction of the operating characteristics of the system from the log K_OW or PDMS/water partition coefficient of the chemical. The system is a simple, safe, predictable and flexible tool that generates stable aqueous concentrations of hydrophobic chemicals.     

Equilibrium partitioning of (14)C-benzo(a)pyrene and (14)C-benazolin between fractionated phases from an arable topsoil

Equilibrium partitioning of hydrophobic (14)C-benzo(a)pyrene and hydrophilic (14)C-benazolin between fractionated phases from an arable topsoil of Merzenhausen (Germany) was investigated. Topsoil samples were collected from lysimeters which were incubated with different residual crops. A physical soil fractionation based on sedimentation and centrifugation steps was performed after water extraction. Four soil phases were obtained designated sediment (SED) phase (>20 microm), microaggregate (MA) phase (2 microm-20 microm), colloid (COL) phase (<2 microm) and electrolyte (EL) phase. The distribution of (14)C-benzo(a)pyrene, (14)C-benazolin and organic carbon between the soil phases was established. Enrichment factors for the two chemicals and organic carbon are higher in the COL and MA phases than in the SED phase. The distribution constant K(d) of chemicals for Merzenhausen topsoil was calculated according to two-phase or three-phase partitioning models. The three-phase partitioning model presumes the contribution of the organic carbon for the binding of chemicals. A log K(oc) of 5.55 can be calculated in the case of (14)C-benzo(a)pyrene, which is typical of the hydrophobic association with the soil organic carbon. In the case of (14)C-benazolin, much higher K(d) and K(oc) values were calculated than found with parent molecules after short-time experiments. Long-term aging processes must be considered. Specific effects on the chemical distribution due to the different crop residues were not detected.     

Uptake of trifluralin and lindane from water by ryegrass

Understanding of the plant uptake of organic chemicals is essential to assessing contaminant mobility in the ecosystem, exposure to humans, and phytoremediation technologies. In this study, we measured the uptake of trifluralin and lindane from water by ryegrass as a function of uptake time for periods of 96 and 120 h, respectively. Trifluralin concentration in ryegrass increased sharply at the early stage of uptake and reached the maximum at 10 h, and then decreased with uptake time. 14C-labelled trifluralin uptake displayed a similar trend but a higher 14C-concentration than that of extracted parent compound, indicating metabolism and formation of bound residues following trifluralin uptake. Lindane concentration in ryegrass slowly increased with uptake time and approached a plateau, indicating minimal metabolism and formation of bound residues. The difference in the uptake characteristics of these two chemicals may be related to the differences in their lipophilicity, and chemical and biological reactivities. A two-compartment model accounting for the contributions of transpiration, metabolism and formation of bound residues to overall uptake was developed to assess the uptake kinetics. The model adequately described the uptake of trifluralin and lindane into ryegrass by providing the first-order rate constants of uptake, release, transpiration, and metabolism and formation of bound residues. These rate constants are used in calculating plant concentration factor (PCF). The ratios of trifluralin concentrations in ryegrass to its aqueous concentrations are between the PCF at thermodynamic equilibrium and the PCF at steady state, suggesting the utility of both PCF values.     

Equilibrium partitioning of PCB congeners in the water column: Field measurements from the Hudson River

The environmental behavior of hydrophobic organic compounds in water is driven by partitioning between dissolved and sorbed phases. Partitioning behavior of a compound is often based on empirical relationships to other properties of the chemical, such as water solubility and octanol-water partition coefficients, but actual partitioning in the environment may differ significantly from such predictions. We conducted intensive studies of the distribution of PCBs in the fresh water portion of the Hudson River, using sensitive capillary-column gas chromatography methods to calibrate and resolve quantitations for 90 PCB congeners in 48 samples at 10 locations. A linear equilibrium model of PCB congener partitioning, when corrected for temperature and suspended-matter organic carbon content, provides a good representation of phase distribution. When particulate-phase concentrations are predicted from dissolved concentrations with a two-phase model, the predictions are unbiased for the majority of samples and the average percent difference between observed and predicted particulate concentrations is ±43 percent. Estimated in situ partition coefficients show systematic differences from partition coefficients predicted from octanol-water partitioning. Partitioning to colloids appears to be a significant component of total concentration for mono- and dichlorobiphenyls, but not for more highly chlorinated congeners.The colloidal fraction may still cause significant overestimation of the bioavailable fraction for more hydrophobic congeners when a two-component model is used.     

Solid phase microextraction as a tool to predict internal concentrations of soil contaminants in terrestrial organisms after exposure to a laboratory standard soil

Uptake and accumulation of three chlorobenzenes was studied in both biota (Enchytraeus crypticus) and 30 mum polydimethylsiloxane (PDMS) solid phase microextraction (SPME) fibers after exposure to spiked OECD soil. The OECD soil was spiked with three different concentrations of all contaminants. Uptake of all three chlorobenzenes in E. crypticus was fast and steady state levels were reached within 2-4 days. Also in the PDMS-SPME fibers uptake was very fast for all three compounds, with steady state levels reached after 1 day. Comparison of steady state levels in biota and in the PDMS-SPME fibers showed a relationship which was consistent over the range of concentrations of chlorobenzenes in soil and the difference in logKow. This shows that measuring the concentrations of hydrophobic chemicals in a hydrophobic phase such as PDMS can be used as a simple tool to estimate internal concentrations of these chemicals in biota exposed to complex matrices such as soil.     

Bioconcentration and biokinetics of heavy metals in the earthworm

This study examines the steady state and non-steady state kinetics of five metals, cadmium, copper, lead, nickel, and zinc in earthworms. The steady state kinetics are based on field studies in which worms from contaminated and uncontaminated sites were collected and measurements were made of concentrations in the earthworms and soils. For each of the metals, evidence suggests that bioconcentration depends on the metal concentrations in the soil; bioconcentration is greater at lower soil concentrations. The studies of non-steady state kinetics involve uptake and elimination experiments in which worms are transferred from an uncontaminated soil to a contaminated soil (uptake studies) or from a contaminated soil to an uncontaminated soil (elimination studies). The voiding time is shown to be an important experimental variable in determining the measured levels of metal in earthworms because experimental measurements are usually made on a worm-soil complex (i.e. the soft tissue of the worm and the soil in the gut of the worm). Thus, for metals that are bioconcentrated in worm tissue, increasing the voiding period increases the concentration of the metal in the worm-soil complex. Conversely, for metals that are not bioconcentrated, increasing the voiding time leads to a decrease in concentrations in the worm-soil complex.     

Statistical uncertainty in hazardous terrestrial concentrations estimated with aquatic ecotoxicity data

Since chemicals’ ecotoxic effects depend for most soil species on the dissolved concentration in pore water, the equilibrium partitioning (EP) method is generally used to estimate hazardous concentrations (HC50) in the soil from aquatic toxicity tests. The present study analyzes the statistical uncertainty in terrestrial HC50s derived by the EP-method. For 47 organic chemicals, we compared freshwater HC50s derived from standard aquatic ecotoxicity tests with porewater HC50s derived from terrestrial ecotoxicity tests. Statistical uncertainty in the HC50s due to limited species sample size and in organic carbon–water partitioning coefficients due to predictive error was treated with probability distributions propagated by Monte Carlo simulations. Particularly for specifically acting chemicals, it is very important to base the HC50 on a representative sample of species, composed of both target and non-target species. For most chemical groups, porewater HC50 values were approximately a factor of 3 higher than freshwater HC50 values. The ratio of the porewater HC50/freshwater HC50 was typically 3.0 for narcotic chemicals (2.8 for nonpolar and 3.4 for polar narcotics), 0.8 for reactive chemicals, 2.9 for neurotoxic chemicals (4.3 for AChE agents and 0.1 for the cyclodiene type), and 2.5 for herbicides–fungicides. However, the statistical uncertainty associated with this ratio was large (typically 2.3 orders of magnitude). For 81% of the organic chemicals studied, there was no statistical difference between the hazardous concentration of aquatic and terrestrial species. We conclude that possible systematic deviations between the HC50s of aquatic and terrestrial species appear to be less prominent than the overall statistical uncertainty.     

Strategies for including vegetation compartments in multimedia models

The incentives for including vegetation compartments in multimedia Level I, II and III fugacity calculations are discussed and equations and parameters for undertaking the calculations suggested. Model outputs with and without vegetation compartments are compared for 12 non-ionic organic chemicals with a wide variety of physical-chemical properties. Inclusion of vegetation compartments is shown to have a significant effect on two classes of chemicals: (1) those that are taken up by atmospheric deposition and (2) those that are taken up by transpiration through the plant roots. It is suggested that uptake from the atmosphere is important for chemicals with logK(OA) greater than 6 and a logK(AW) of greater than -6. Plant uptake by transpiration is important for chemicals with logK(OW) less than 2.5 and a logK(AW) of less than -1. At logK(OA) > 9 atmospheric uptake is dominated by particle-bound deposition and the importance of partitioning to vegetation is largely dependent on the relative magnitude of the particle deposition velocities to soil and vegetation. These property ranges can be used to determine if a chemical will significantly partition to vegetation. If the chemical falls outside the property ranges of the two classes it will probably be unnecessary to include vegetation in models for assessing environmental fate. The amount of chemical predicted to partition to vegetation compartments in the model is shown to be highly sensitive to certain model assumptions. Further experimental research is recommended to obtain more reliable equations describing equilibrium partitioning and uptake/depuration kinetics.     

Correlations between experimental and predicted equilibrium distribution coefficient of chlorobenzene and chlorophenol compounds in soil-water systems using partial solubility parameters

Many pesticides are degraded to become chlorinated aromatic compounds in soils. Equilibrium distribution of chlorobenzene and chlorophenol compounds in soil-water systems of Yangmingshan loam, Pingcheng silty clay loam and Annei silty loam was studied with the integral distribution equilibrium equation involving the partial solubility parameters of the chemicals. If the adsorption of chemicals on soils is partitioning in soil organic matter surrounding the soil mineral particles, the absorption constant (Kd) of a chemical in soil-water system could be stated as the distribution coefficient (or partition constant, Koc) of the chemical in the two adjunct immiscible phases--water and soil organic matter. The distribution coefficient (Koc) of chemicals calculated from the integral distribution equilibrium equation agrees well with the experimental adsorption coefficient (Kd, or experimental Koc) of chemicals determined in this study, for all the three different types of soils in water according to multiple-regression analysis. Reference data of Karger or Tijssen are employed to estimate the Koc for both polar and non-polar chemicals. The integral distribution equilibrium equation can exactly describe the distribution behavior of nonionic compound of chlorobenzenes and chlorophenols in soil-water systems.     

Bioaccumulation and elimination of 14C-lindane by Enchytraeus albidus in artificial (OECD) and a natural soil

Bioaccumulation and elimination of 14C-lindane in Enchytraeus albidus was studied in artificial OECD soil and a silty loam from an agricultural field in Central West Portugal. Results showed that enchytraeids were able to bioaccumulate the chemical with a kinetic pattern similar to that of earthworms: fast uptake within a few days and a biphasic elimination pattern. A 10 day period to study uptake was sufficient, but a few more days were probably necessary for elimination. Bioaccumulation was influenced by soil type. The authors suggest that higher organic matter (OM) content and also the higher content on sand particles in the OECD soil may have led to a faster elimination: hydrophobic chemicals tend to adsorb to OM being in this way less bioavailable and therefore less bioaccumulated having bioaccumulation factor value around 6 while in natural soil is 10; the sand could act as abrasive particles (helpers) in the elimination process leading to an elimination of 90% of the chemical in two days while in natural soil 67% was eliminated in the same period of time.     

Enhanced desorption of phenanthrene from soils using hydroxypropyl-beta-cyclodextrin: experimental results and model predictions

Objective of this study was to evaluate the effects of hydroxypropyl-beta-cyclodextrin (HPCD) on the removal of phenanthrene from solid phase. Batch tests for the phenanthrene distribution between aqueous and solid phase were conducted in the presence of HPCD. Column tests and numerical simulations were conducted to evaluate the roles of HPCD cavities and interaction rates between water, HPCD, and solid phase in the enhanced removal of phenanthrene. Experimental results showed that HPCD was effective in removing sorbed phenanthrene from subsurface environment, primarily due to its negligible sorption to the solid phase and the partitioning of phenanthrene into HPCD cavities. From the numerical simulations, it was found that rate-limited partitioning of phenanthrene into HPCD cavities was most influential factor in the enhanced elution of phenanthrene. Sorption and desorption rate of phenanthrene between aqueous and solid phase was very fast or near equilibrium state. Interaction rates of contaminant between water, HPCD, and solid phase could be affected by other factors such as soil types and organic matter contents. Results from this study implied that HPCD flushing could be effectively applied for the removal of hydrophobic organic pollutants existing in the soils as sorbed or NAPL state.     

Ozonation of azo dye Acid Red 14 in a microporous tube-in-tube microchannel reactor: decolorization and mechanism

Despite the great success of time-weighted average passive sampling of hydrophobic contaminants, such as PCBs and PAHs, the sampling of polar organic compounds still presents a challenge because the equilibrium between water and most sampling phases is attained in a relatively short time. In this study, we proposed a new time-integrative sampler using in situ solvent extraction (TISIS) for polar organic chemicals. The sampler was composed of a 15 cm poly(dimethylsiloxane) (PDMS) tubing, with an internal diameter of 0.5 mm and wall thickness of 0.5 mm, through which an extraction solvent (acetonitrile) was passed. Four polar organic contaminants, caffeine, atrazine, diuron and 17α-ethynylestradiol, were chosen for the evaluation of the performance of the sampler. Without the use of in situ solvent extraction, the PDMS tubing when exposed to a constant aqueous concentration of the four model compounds was able to linearly accumulate those compounds for less than 12 h and equilibrium between the PDMS tubing and water was attained in 2 d under our laboratory conditions. However, TISIS when exposed to a constant aqueous concentration was able to linearly accumulate all the model compounds without any exposure time limitation. The measured sampling rates at three different extraction flow rates (0.2, 0.5, 1.5 mL min⁻¹) were similar, regardless of the chemicals, indicating that the overall mass transfer from aqueous solution to the extraction solvent was most likely dominated by partitioning to the PDMS tubing and the internal diffusion within PDMS. In addition, a pulsed exposure experiment confirmed that TISIS operated in a time-integrative mode when the environmental concentration was highly fluctuated.     

The extent of multimedia partitioning of organic chemicals

This paper examines the question of the extent of multimedia partitioning of organic chemicals. Partition profiles are estimated for releases into air, water, and soil. The analysis shows that cross-media partitioning can be expected for 50 – 80 % of all organic chemicals.     

Enhanced Desorption of Phenanthrene from Soils Using Hydroxypropyl‐β‐cyclodextrin: Experimental Results and Model Predictions

Objective of this study was to evaluate the effects of hydroxypropyl‐β‐cyclodextrin (HPCD) on the removal of phenanthrene from solid phase. Batch tests for the phenanthrene distribution between aqueous and solid phase were conducted in the presence of HPCD. Column tests and numerical simulations were conducted to evaluate the roles of HPCD cavities and interaction rates between water, HPCD, and solid phase in the enhanced removal of phenanthrene. Experimental results showed that HPCD was effective in removing sorbed phenanthrene from subsurface environment, primarily due to its negligible sorption to the solid phase and the partitioning of phenanthrene into HPCD cavities. From the numerical simulations, it was found that rate‐limited partitioning of phenanthrene into HPCD cavities was most influential factor in the enhanced elution of phenanthrene. Sorption and desorption rate of phenanthrene between aqueous and solid phase was very fast or near equilibrium state. Interaction rates of contaminant between water, HPCD, and solid phase could be affected by other factors such as soil types and organic matter contents. Results from this study implied that HPCD flushing could be effectively applied for the removal of hydrophobic organic pollutants existing in the soils as sorbed or NAPL state.     

杀虫剂十氯酮的多介质环境行为模拟

应用EQC模型模拟十氯酮在多介质环境中的归宿和迁移通量.结果表明:土壤是十氯酮最大的贮存库,在稳态平衡条件下,残留率达到95.0%;在稳态非平衡条件下,十氯酮单独排放到水体,有37.5%残留在于排放的水体中,其在大气的浓度水平和质量分布均很低,在沉积物中的质量则来自于水体向沉积物的沉降迁移;十氯酮主要通过水体的水平迁移和土壤的厌氧降解输出;十氯酮的主要界面迁移过程是大气向土壤的迁移,其次是水体向沉积物的沉降和大气向水体的迁移.     

Grinding and sieving soil affects the availability of organic contaminants: a kinetic analysis

Field contaminated soils are often homogenized before application in bioassays and chemical assays that estimate the (bio)availability of their contaminants. The homogenization of the soil might affect the availability, and thereby the outcome of a bioassay might not reflect field situations. In this study, uptake kinetics of polycyclic aromatic hydrocarbons (PAH) by a negligible depletive passive sampler exposed to a ground and non-ground field contaminated soil were tested. The measurements illustrate how freely dissolved pore water concentrations of contaminants can be affected by soil treatment. It took more than a month, and over a year to reach steady state in the passive sampler exposed to the ground and non-ground soil, respectively. The uptake rate seemed to be limited by desorption from the soil, even though the fiber only extracted 0.2% of the soil-sorbed PAH at maximum. If these observations are translated to the field situation, where contaminants are not homogeneously distributed and disappear by (bio)degradation or physical transport processes, it is unlikely that pore water concentrations are solely determined by a thermodynamic equilibrium. Hence, exposure of organisms in these soils cannot always be estimated by sorption studies and an equilibrium partitioning approach.