Bioconcentration of superlipophilic persistent chemicals

According to present understanding, persistent superlipophilic chemicals — such as octachlorodibenzo-p-dioxin, octachlorodibenzofuran, Mirex etc — with log K_ow > 6 and cross sections > 9.5 Å, bioconcentrate in aquatic organisms only little from ambient water. The most convincing argument against it is that in bioconcentration experiments with superlipophilic chemicals amounts applied exceeded water solubility by several orders of magnitude. This paper describes various methods for determining bioconcentration factors (BCF) of superlipophilic compounds. As exemplified with octachlorodibenzo-p-dioxin, BCF values evaluated by these methods match well with those calculated by QSARs for fish and mussels based on log K_ow and water solubility. As expected, these BCF values exceed previous values by several orders of magnitude. For BCF evaluation of superlipophilic chemicals in aquatic organisms we recommend:

1. flow-through systems, kinetic method (OECD guideline No. 305 E)
2. ambient concentrations < water solubility
3. during the uptake and especially during the elimination phase no toxic effects of the test organisms should occur.

     

Environmental risk assessment of existing chemicals

Most of the existing chemicals of high priority have been released into the environment for many years. Risk assessments for existing chemicals are now conducted within the framework of the German Existing Chemicals Program and by the EC Regulation on Existing Substances. The environmental assessment of a chemical involves:

1. exposure assessment leading to the derivation of a predicted environmental concentration (PEC) of a chemical from releases due to its production, processing, use, and disposal. The calculation of a PEC takes into account the dispersion of a chemical into different environmental compartments, elimination and dilution processes, as well as degradation. Monitoring data are also considered.
2. effects assessment. Data obtained from acute or long-term toxicity tests are used for extrapolation on environmental conditions. In order to calculate the concentration with expectedly no adverse effect on organisms (Predicted No Effect Concentration, PNEC) the effect values are divided by an assessment factor. This assessment factor depends on the quantity and quality of toxicity data available.

In the last step of the initial risk assessment, the measured or estimated PEC is compared with the PNEC. This “risk characterization” is conducted for each compartment separately (water, sediment, soil, and atmosphere). In case PEC > PNEC an attempt should be made to revise data of exposure and/or effects to conduct a refined risk characterization. In case PEC is again larger than PNEC risk reduction measures have to be considered.     

Guide values for contaminated sites in Baden-Württemberg

The treatment of hazardous sites in Baden-Württemberg is based on three legal documents: the state waste disposal art (LAbfG, 1990), the assessment committee directive (KommissionsVO, 1990), and the guide values directive (UM & SM B-W, 1993). The guide values directive was commonly issued by the Ministry of Labor, Health and Social Affairs and the Ministry of the Environment of the state of Baden-Württemberg (UM & SM B-W, 1993) and contains a three-level hierarchy of numerical criteria and rules which serve as both screening levels during the investigation and as remediation objectives. The decision for the appropriate level of remediation is based on feasibility and environmental balance considerations. The levels are ordered as follows:

? Level 1 (Background-Values) On principle, all remediations have to be based first on background levels. In the case of lack of feasibility or negative environmental balance for level-1 objectives use-specific requirements are considered next.

? Level 2 (Assessment-Values for Worst Case Exposure Conditions) The generic requirements underlying level 2 afford appropriate protection for humans regarding the most sensitive uses of the environment. At least four resources are considered on this level: Ground-water as such and its use, the health of humans on contaminated sites, and soil with respect to growth and quality of plants. Barriers against migration of the contaminants, the effect of dilution, and abandonment of certain uses, etc., are not taken into consideration on level 2.

? Level 3 (Site-Specific Requirements) Lack of feasibility or a negative environmental balance of level-2 objectives lead to consideration of site-specific circumstances which may alleviate the requirements. With respect to groundwater, the distinction is again necessary between groundwater as a resource and the use of groundwater. On level 3 the guideline gives rules of how to derive site-specific remediation objectives for groundwater in the form of concentrations and fluxes of contaminants after taking into account barriers, dilution, and the abandonment of uses.

The guideline is the only directive of its kind in the world that regulates both concentrations and fluxes of contaminants into groundwater.     

Continuous four-dimensional source attribution for the Berlin area during two days in July 1994. Part II: Sensitivity studies

The multiple nested three-dimensional (3D) mesoscale Eulerian grid point model MM5 is directly coupled with a Lagrangian particle trajectory model in order to perform a four-dimensional source attribution for the area of Berlin based on the horizontal distribution of the import probability density (IPD). The technical aspects are already demonstrated in the companion paper A (Part I) including the illustration of the meteorological situation at the two consecutive days of investigation and a primarily 3D source attribution. We conducted further sensitivity studies concerning the effect of vertical mixing, the static stability of the particles/emissions and the regarded time scale on the IPD distribution which is extended to four dimensions. The main results are:

• •Heterogeneity and temporal variability of the wind field enhance the contributions of nearby sources (emissions) to the total import of the receptor in contrast to stationary wind fields which increase the scope of the IPD distribution in the upstream direction.
• •Regions of static stability, for example morning hour inversion layers, enhance the contribution of far distance sources with longer import times.
• •The import velocities increase, as far as long distance source-receptor transitions are concerned, because they are mostly realised via higher transport paths.
• •The third (vertical) dimension is not negligible for the task of a complete source attribution, as a considerable amount of elevated emissions, preferably out of 300±100 m elevation, reaches the receptor box which is only 50 m in depth. Hence, downward mixing of elevated and far distance sources is an important process and driven by the diurnal course of turbulence and low level jets within the PBL
• •On the short time scale (few days), the source attribution is not independent from the regarded time scale (simulation time) due to the neglecting of older emissions released before the beginning of the simulation.

     

Individual PCBs as predictors for concentrations of non and mono-ortho PCBs in human milk

32 Dutch human milk samples were analyzed for PCBs with either HRGC-ECD or HRGC-LRMS in the NCI mode. Samples were collected from three different locations in The Netherlands: Amsterdam, Rotterdam and Groningen. Quantitatively, no differences could be observed between the three localities, while in addition the congener specific pattern showed a striking similarity for all individual samples. Only principal component analysis revealed slight individual differences. Based on similarities in the PCB profiles, linear relationships were calculated between 2,3′4,4′,5-PnCB (#118) or 2,2′4,4′5,5′HxCB (#153) and the most relevantnon andmonoortho PCBs exhibiting dioxinlike activity. These PCBs included 2,3,3′,4,4′-PnCB (#105), 3,3′,4,4′5-PnCB (#126) 2,3,3′,4,4′,5-HxCB (#156), 2,3,3′,4,4′,5′-HxCB (#157), 2,3′,4,4′,5,5′-HxCB (#167) and 3,3′,4,4′,5′5-HxCB (#169). Good linear relationships were observed between individual PCBs. Based on the results of this study, PCB #118 can be used to predict concentrations of the PCBs #105 and #126. PCB #153 can be used as a predictor for the PCBs #156, #157, #167 and #169, but also for the total toxic equivalencies (TEQs) ofnon andmonoortho PCBs present in human milk. This method using certain PCBs as predictors for other toxicological relevant congeners, can be useful and cost effective, e.g. for epidemiological studies. However, before applied a number of conditions should be met. These are:

1. A stable composition of the PCB matrix should be established.
2. A possible time dependent change in composition of the matrix should first be excluded when used over different time periods.

     

Continuous four-dimensional source attribution for the Berlin area during two days in July 1994. Part I: the new Euler–Lagrange-model system LaMM5

The multiple nested three-dimensional mesoscale Eulerian grid point model MM5 was directly coupled with a Lagrangian particle trajectory model in order to perform a four-dimensional source attribution for the area of Berlin based on the import probability density (IPD) distribution of the according receptor box. Within the resulting model system LaMM5 introduced here, the IPD distributions are not based on backward trajectories, which lack the recognition of the turbulent environment, but on the forward integration of a huge amount (order of Million per day) of particle releases according to an emission scenario which is approximately continuous in space and time. Hence the receptor import record yields an accordingly continuous IPD distribution. Much attention has been paid on spatial and temporal resolution at the interface between both model parts (online-coupling) and the interface itself has been extended by the turbulent quantities resulting from the higher-order turbulence closure of the Eulerian model part. LaMM5 is applied on an episode with high photochemical activity across Berlin at two consecutive days (25th and 26th of July in 1994) with varying meteorological conditions leading to an accordingly different source attribution. The main results are:

• •The decay of the Berlin IPD with increasing source-receptor distance and time appears in an exponential manner if only sources out of a constant level (z=25 m) are regarded.
• •Heterogeneous wind fields in time and space enhance the contributions (emissions) of nearby sources to the total import of the receptor in contrast to stationary wind fields which increase the scope of the IPD distribution in upstream direction.

There are further results from several additional sensitivity studies presented in a companion paper B (Part II).     

Erratum to “Continuous four-dimensional source attribution for the Berlin area during two days in July 1994. Part I: The new Euler–Lagrange-model system LaMM5”: [Atmospheric Environment 35 (32) (2001) 5497]

The multiple nested three-dimensional (3D) mesoscale Eulerian grid point model MM5 was directly coupled with a Lagrangian particle trajectory model in order to perform a 4D source attribution for the area of Berlin based on the import probability density (IPD) distribution of the according receptor box. Within the resulting model system LaMM5 introduced here, the IPD distributions are not based on backward trajectories, which lack the recognition of the turbulent environment, but on the forward integration of a huge amount (order of million per day) of particle releases according to an emission scenario which is approximately continuous in space and time. Hence, the receptor import yields an accordingly continuous IPD distribution. Much attention has been paid on spatial and temporal resolution at the interface between both model parts (online-coupling) and the interface itself has been extended by the turbulent quantities resulting from the higher-order turbulence closure of the Eulerian model part. LaMM5 is applied on an episode with high photochemical activity across Berlin at two consecutive days (25 and 26 July 1994) with varying meteorological conditions leading to an accordingly different source attribution. The main results are:

• •The decay of the Berlin IPD with increasing source-receptor distance and time appears in an exponential manner if only sources out of a constant level (z=25 m) are regarded.
• •Heterogeneous wind fields in time and space enhance the contributions (emissions) of nearby sources to the total import of the receptor in contrast to stationary wind fields which increase the scope of the IPD distribution in upstream direction.

There are further results from several additional sensitivity studies presented in a companion paper B (Part II).     

Toxicity testing of highly volatile chemicals with green algae

A gas-tight system for toxicity testing of highly volatile chemicals with the green algaChlamydomonas reinhardtii was developed. The procedure permits maintenance of constant and defined concentrations of the tested compounds in the vessels. To ensure sufficient CO₂-supply, new bipartite test vessels were used. These vessels allowed spatial separation of a HCO₃-/CO ₃ ^2? buffer used for CO₂ supply and the alga culture to avoid growth inhibition due to ionic strength. Several volatile chlorinated hydrocarbons have been tested. Their EC10 values were several orders of magnitude lower than those obtained with open test systems.     

Isolation and Identification of Antialgal Compounds from the Leaves of Vallisneria spiralis L. by Activity-Guided Fractionation (5 pp)

Background, Aims and Scope

Vallisneria spiralis Linn., a common, submerged macrophyte, is widely available in quiet waters of lakes, ponds, marshes and streams in Southeast Asia. V. spiralis plays a significant role not only in decreasing eutrophication of water body for its productivity, but also in inhibiting the growth of blue-green algae? The aim of the paper involves the isolation and identification of allelochemicals from extracts of V. spiralis by activity-guided fractionation and column chromatography.

Methods

Leaves of V. spiralis was washed free of debris, air-dried and refluxed in 95% EtOH. The extract was isolated using column chromatography and fractionation with antialgal activity. Potential allelochemicals were analyzed by high-resolution gas chromatography-mass spectrometry (HRGC-MS).

Results

Two fractions with strong antialgal activity were isolated using column chromatography and activity-guided fractionation from the extract of V. spiralis. 2-Ethyl-3-methylmaleimide, dihydroactinidiolide and 4-oxo-β-Ionone were identified in the first fraction, and 3-hydroxy-5,6-epoxy-β-ionone, loliolide, 6-hydroxy-3-oxo-α-ionone and an unknown compound in the second fraction. They had strong inhibitory effects on Microcystis aeruginosa Kütz.

Discussion

2-Ethyl-3-methylmaleimide is a byproduct of photooxidation of chlorophyll, and five other compounds identified were derivatives of β-carotene. HRGC-MS and derivatization technology were used to identify and confirm their molecular structures. The formula of the unknown compound was C16H19NO4. Metabolites of plant pigments had strong inhibitory activities on growth of algae.

Conclusions

Six compounds had been identified in V. spiralis, among them, 2-ethyl-3-methylmaleimide was the main allelochemical, and derivatives of ionone were also potential allelochemicals.

Recommendations and Perspective

. The results of our research could help us to study further mechanisms of inhibitory effect on algae and develop new potential antialgal substances.     

Behavioural ecotoxicology,an “early warning” signal to assess environmental quality

Background

In this review, the position of behavioural ecotoxicology within the available means to assess the status of marine environments is described as filling the gap for the needed “early warning” signals. A few examples of studies performed since the 1960s are discussed to highlight the sensitivity of these approaches in investigating the effects of chemicals, including priority pollutants and emerging contaminants, relative to conventional toxicity tests measuring survival.

Discussion

The advantage of the behavioural response is due to the integration of biochemical and physiological processes that reflect changes at higher levels of organisation with ecological relevance. Avoidance often represents a behavioural symptom easily detected in many animals exposed to contaminants and would be a useful test to explore more widely. This rapid response would reflect a defence mechanism protective against further exposure and the potential development of more pronounced deleterious effects, whilst in some cases, escape could lead to the relocation of a species with negative consequences. An investigation of the avoidance behaviour of mud shrimp, Corophium volutator, along with the chemical analyses of sediments and amphipods to assess the quality of harbour sediments is summarised. The body burden of the amphipods was 1,000 times lower than the one associated with narcosis, emphasizing the sensitivity of this endpoint. The application of this acute toxicity test is briefly compared to additional work that involved intertidal mussels collected in the field.

Conclusions

Recent research undertaken with mud snails, Ilyanassa obsoleta, and harbour sediments confirmed the usefulness of the escape behaviour as an assessment tool. However, the limits of the state of knowledge regarding the fate of contaminants in species with the ability to metabolise contaminants is further discussed along with directions to be pursued to address questions arising from the reviewed literature.

     

SCRAM: A scoring and ranking system for persistent, bioaccumulative, and toxic substances for the North American Great Lakes

Hundreds of chemical contaminants have been identified in the Great Lakes System of North America. Depending on the agency or organization, various subset lists of these contaminants have been identified as chemicals of potential concern. However, there is no agreement on the method that should be used to make management decisions. Except for consensus on approximately 40 chemicals that most North American agencies agree can cause deleterious effects if released into the environment, no agreement has been reached regarding the priority that contaminants should receive for further action. That leaves hundreds of chemicals that have been, are being, or potentially could be released into the environment that have not been evaluated yet. A profile for potential chemicals of concern is generally thought to include persistence in the environment, potential to bioaccumulate, and ability to cause toxic effects at environmentally relevant concentrations. Except for the International Joint Commission’s definition of persistence (> 8 weeks residence time in air, water, soil or sediment), there is little concurrence about what defines these characteristics. For instance, the State of Michigan currently has no established definitions or profiles of persistent, bioaccumulative, toxic substances. Furthermore, there is no standard process to rank chemicals relative to these characteristics. The Chemical Scoring and Ranking Assessment Model (SCRAM) has been developed to provide a process to rank-order chemicals based on these characteristics. The SCRAM system was developed primarily for use in the Great Lakes region of North America and particularly in Michigan, but it is not site-specific. Use of this system may assist in pollution prevention activities and other future chemical control efforts, allowing attention to be focused first on those chemicals likely to present the greatest hazard.     

Twenty-five years of biomonitoring lead in the Frankfurt/Main area

The present study is an example of the historical monitoring of heavy metals. The specific question it aims to explore is: to what extent has the lead content of selected organisms used for biomonitoring in Frankfurt/Main—one of the cities in Germany most heavily affected by automobile traffic—changed as a result of legislation on leaded gasoline?

Data on the lead content of the moss speciesBryum argenteum Hedw. from the years 1974, 1975 and 1978 and data on the lead content of the outer bark of the ash speciesFraxinus excelsior L. from 1973 served as the basis for the repeated measurements. Remeasurement was successful in 76.5% (i.e. 124 trees at 26 growth sites). The study produced the following results:

• ? As was expected, the lead content of the short-term accumulatorBryum argenteum Hedw. was distinctly lowered with a decreasing particulate lead concentration. However, the reduction factor varied greatly between the different growth sites.
• ? On the other hand, the lead content measured in the outer bark layers ofFraxinus excelsior L. has risen markedly during the past two decades. Whereas in 1973 nearly all trees examined displayed very low concentrations of lead (< 38 ppm), only 9.5% were still in this category in 1997 and nearly 30% exhibited high or even unacceptable lead concentrations (< 150 ppm → > 225 ppm). Various factors have to be taken into account to explain this increase. First of all, bark is a long-term accumulator for heavy metals like lead and its enrichment capacity could have increased as the surface becomes rougher over time. Furthermore, lead is most probably leached out of the bark to a lesser degree now than in the 1970s, owing to the reduced concentration of sulphuric acid in the rain. The dramatic growth of automobile traffic in the Frankfurt/Main area during the period covered by the study undoubtedly plays an important role as well.

     

Environmental Hazard- Assessment of chemicals and products

Part II: Persistence and Degradability of Organic Chemicals The criteria “Persistence” and “Degradability” are defined and explained, starting from the “functional” definition of the environment. In this definition, theenvironment is the counterpart of thetechnosphere, which consists of all processes controlled by man. A substance is persistent if there are no sinks (degradation processes). It is shown that persistence is the central and most important critérium of environmental hazard assessment of organic chemicals. It follows that all substances released into the environment should be degradable, preferentially into small inorganic molecules (mineralization). As examples for persistent substances, the polychlorinated biphenyls (PCB), the chlorofluorohydrocarbons (CFC), bis (2-ethylhexyl) phthalate (DEHP), and 2,3,7,8-tetrachloro-dibenzo-dioxin (TCDD) are discussed. Finally, an attempt to quantify persistence is made.     

Environmental hazard — Assessment of chemicals and products

Part III: The Limits to Single Compound Assessment The principles and basic assumptions of single compound assessment are briefly reviewed. Limitations to this approach are shown, especially with regard to complex mixtures of similar substances, substitution products, and complicated (final) products containing chemicals and materials produced by the chemical industry. A new thinking in product lines and life cycles is emerging, leading to new assessment methods. In some cases, substitution has not improved the environmental performance of products, since very similar chemicals were used as substitutes.     

Tissue concentrations, bioaccumulation, and biomagnification of synthetic musks in freshwater fish from Taihu Lake, China

Synthetic musks are ubiquitous pollutants in aquatic environments. As hydrophobic chemicals, they can accumulate in terrestrial and aquatic organisms. Investigations into the bioaccumulation of these chemicals in aquatic ecosystem have, however, been limited, and previous results were inconsistent among species and ecosystem. Studies on this topic have been carried out in European countries, the USA, and Japan, but very few are known of the situation in China. The aim of this study was to investigate contaminant levels of musks in fish from Taihu Lake, the second largest freshwater lake in China, as well as bioaccumulation and biomagnification of the pollutants in the freshwater food chain. Five polycyclic musks and two nitro musks were determined in 24 fish species and nine surface sediment samples from Taihu Lake. HHCB (1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta[γ]-2-benzopyran) and AHTN (7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene) were the predominant contaminants in the fish samples, with concentrations ranging from below the limit of detection (LOD) to 52.9 and from <LOD to 7.5 ng/g lipid weight, respectively. Other contaminants were at low detection frequencies. The results indicated low concentrations of musks yet widespread occurrence of these contaminants in fish from Taihu Lake. Species-specific and lipid-related bioaccumulation characteristics were suggested, but no significant region-specific differences were observed. Normalized biota-sediment accumulation factors for HHCB and AHTN were noted to increase with trophic levels in fish. Trophic magnification factors were estimated at 1.12 for HHCB and 0.74 for AHTN. A biomagnification for HHCB, and probably biodilution for AHTN, in the freshwater food chain are indicated, when trophic magnification factors were concerned. However, the correlations between logarithmic concentrations of the chemicals and trophic levels were not statistically significant. Further study using long food chains in this lake is still needed.     

Dietary and environmental estrogens and antiestrogens and their possible role in human disease

Recent reports have suggested that dietary and environmental estrogens such as organochlorine pollutants may play a role in the increased incidence of breast cancer in women and disorders of the male reproductive tract. For example, elevated levels of DDE and polychlorinated biphenyls (PCB) have been measured in women with breast cancer. However, it should also be noted that numerous environmental and dietary compounds have also been characterized as antiestrogenic and as inhibitors of mammary cancer cell growthin vitro and/orin vivo. Some of these compounds include 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) and related compounds, polynuclear aromatic hydrocarbons (PAH), other naturally-occurring TCDD receptor agonists, retinoids, phorbol esters, terpenes, fatty acids, and polysaccharides. Thus, it is possible that dietary and environmental estrogens and antiestrogens may be contra-active, and these interactions must be considered in the overall risk assessment of the potential adverse human and environmental health impacts of these chemicals.