Immunoassay monitoring of polychlorinated biphenyls (PCBs) in the Great Lakes

Although polychlorinated biphenyls (PCBs) are no longer manufactured, they are still entering the environment. In some compartments of the environment, PCB concentrations are a serious concern. This is especially true in compartments which accumulate PCBs, and in food items consumed by humans and wildlife. Also, there are situations in which management decisions require rapid, sensitive, accurate measurements, which can be made in real time under field conditions. Methods to use an enzyme-linked immunosorbent assay (ELISA) for PCBs were developed and applied to sediments and fish muscle homogenates collected from the Great Lakes. The extraction methods developed can be applied in the field with non-hazardous solvents, in the absence of sophisticated laboratory equipment. The method detection limit for PCBs in dimethyl sulfoxide (DMSO) extracts of sediment was 0.9 mg/kg. For PCBs in isopropanol extracts of fish tissue, the method detection limit was 0.6 mg/kg. The resolution of the ELISA was 0.83 mg/kg at 1.1 mg/kg and 1.6 mg/kg at 1.7 mg/kg, for sediment and fish tissue, respectively.     

Surfactant solubilization of hydrophobic compounds in soil and water

Reductions in the apparent soil-water partition coefficients (K_d ^*) for 28 polychlorinated biphenyls (PCBs) caused by the surfactant sodium dodecylsulphate (SDS) in the aqueous phase were studied. Above the critical micelle concentration (CMC) of the surfactant, K_d ^* was reduced by 2–3 orders of magnitude, but even far below CMC at environmentally relevant surfactant concentrations significant reductions in K_d ^* were observed. The plot of the soil-water partition coefficient (K_d) divided by K_d ^* versus the concentration of SDS allowed for the calculation of monomer (K_mn ^oc) and micellar (K_mc ^oc) surfactant-water partition coefficients normalized to organic carbon for each PCB congener. K_mn ^oc values were comparable with published values for the partition of PCBs between natural dissolved organic matter and lake water. K_mc ^oc values were up to 30 times higher than K_mn ^oc values and comparable with published octanol-water distribution coefficients. The findings of the present study underline the potential of surfactants at concentrations below their CMC to mobilize otherwise strongly bound hydrophobic compounds in soil-water systems.     

Deposition of semivolatile organic compounds to spruce needles

The deposition of atmospheric tetrachlorobenzene, pentachlorobenzene, hexachlorobenzene, α-HCH, γ-HCH, DDT, DDE and the PCB congeners 52, 101, 138, 153 and 180 to spruce needles (Picea abies) was estimated for a period of 9 months. Accumulation in spruce as a result of dry gaseous deposition, particle bound deposition and wet deposition was calculated on the basis of the corresponding deposition rates and the compounds’ concentrations in the different atmospheric compartments. The comparison of the calculated values with the concentrations of the compounds measured in 9-month-old spruce needles showed that for many compounds each deposition pathway could explain a large part of the concentrations found in the needles.     

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.     

Uptake and metabolism of 2,4,6-trinitrotoluene in higher plants

The fate of the explosive 2,4,6-TNT in plants is of major interest. Therefore, a method was developed to analyse TNT and derivatives in plant tissue. The method was utilized to investigate the uptake and metabolism of TNT inMedicago sativa andAllium schoenoprasum grown in hydroponic cultures containing TNT levels of 0.1 to 10 mg/1. Detectable concentrations of nitrotoluenes were significantly higher inAllium schoenoprasum than inMedicago sativa. The uptake of TNT in plants was directly related to the initial TNT level. The principal nitroaromatic components in roots and shoots of both plant species were identified as 4-ADNT and 2-ADNT in equal amounts, with substantially less TNT.     

Levels of glyphosate in surface waters, sediments and soils associated with direct sowing soybean cultivation in north pampasic region of Argentina

Levels of glyphosate were determined in water, soil and sediment samples from a transgenic soybean cultivation area located near to tributaries streams of the Pergamino-Arrecifes system in the north of the Province of Buenos Aires, Argentina. Field work took into account both the pesticide application and the rains occurring after applications. The pesticide was analysed by HPLC-UV detection, previous derivatization with 9-fluorenylmethylchloroformate (FMOC-Cl). In addition, SoilFug multimedia model was used to analyse the environmental distribution of the pesticides. In the field, levels of glyphosate in waters ranged from 0.10 to 0.70mg/L, while in sediments and soils values were between 0.5 and 5.0mg/Kg. Temporal variation of glyphosate levels depended directly on the time of application and the rain events. The results obtained from the application of the model are in accordance with the values found in the field.     

Polychlorinated dibenzo-p-dioxins (PCDDs) and furans (PCDFs) in urban air and deposition in the United Kingdom

Polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) have been monitored in air and deposition at four UK urban sites (London, Cardiff, Manchester and Stevenage) since the beginning of 1991; data from the first 2 years are presented here. Median Σ2,3,7,8-substituted PCDD/F concentrations in air were 3.2, 4.0, 3.5 and 2.6 pg/m³ respectively for London, Cardiff, Manchester and Stevenage. Median Σ2,3,7,8-substituted PCDD/F deposition fluxes were 1.5 ng/m²/day in London, 1.4 ng/m²/day in Cardiff and Manchester and 0.79 ng/m²/day in Stevenage. Seasonal variations in the PCDD/F concentrations were observed at all sites for both air and deposition, with concentrations/fluxes generally elevated during the winter.     

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.     

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.     

Determination of atrazine in rainfall and surface water by enzyme immunoassay

Rainwater and surface water from four sites in Germany (Bavaria and Lower Saxony) were analyzed for atrazine by enzyme immunoassay from June 1990 until October 1992. The limit of quantification of the immunoassay was 0.02 μg/L with a middle of the test at 0.2 μg/L. About 60 % of the samples contained measurable amounts of atrazine. Seasonal trends were observed, with the highest concentration in the summer months of up to 4 μg/L for rainwater and up to 15 μg/L for surface waters. The highest concentrations were found in agricultural areas, while in the investigated national parks up to 0.56 μg/L could be detected in rain water. This points to long-range atmospheric transport from agricultural areas to pristine national parks. Samples from forest stands usually showed higher atrazine concentrations than samples from open fields. Deposition rates of 10 – 50 μg/m² · yr were observed in the national parks and 10–180 μg/m² · yr at the agricultural sites. Comparison of results obtained by enzyme immunoassay and GC/MS showed a good correlation of r = 0.95.     

Determination of microbial activity in activated sewage sludge by dimethyl sulphoxide reduction

A method was developed to determine the dimethyl sulphoxide (DMSO) reduction rate in activated sewage sludge at nearly natural conditions. Linearity of microbially produced dimethyl sulphide with incubation time and sample size was shown. Apart from a fast, sensitive and highly reproducible automatic analysis of dimethyl sulphide, simultaneous determination of mineralisation, respiration and phenol degradation rates was possible. The DMSO reduction rate of samples taken from a municipal sewage plant ranged between 2 and 3 μmol/(g dry matter · h), respiration and mineralisation rates between 30 and 80 μmol/(g · h). Added¹³C₆-phenol was completely degradated after 96 h of incubation. A half-life of 14 h was calculated assuming first order decay. Dose response curves were obtained by incubating samples for 2, 6, 25, and 96 hours after addition of pentachlorophenol. At an incubation time of 6 h, the EC₅₀ values ranged from 20 mg/L (DMSO reduction) to 30 mg/L (phenol degradation) up to 180 mg/L (respiration and mineralisation). Increasing the incubation time to 96 h resulted in a lower EC₅₀ of 9 mg/L for DMSO reduction, whereas it increased to 500 mg/L for respiration and mineralisation.     

Observations on long-term air-soil exchange of organic contaminants

Evidence for long-term changes in the soil composition of selected organic compounds, brought about by exchanges with the atmosphere, is briefly reviewed. In the case of some compounds — such as benzo(a)pyrene and octachlorodibenzo-p-dioxin, soils may be significant long-term environmental sinks for atmospherically-derived material. In other cases — such as phenanthrene and some of the lighter PCBs, de-gassing or volatilisation from soil back to the air can occur under certain conditions. Hence the soil may act as a “short-term” sink, and a potential source to atmosphere. Indeed, for some ‘semi-volatile’ compounds used in large quantities in the past — such as PCBs, soil outgassing may actually be an extremely important source to contemporary air. Furthermore, soil outgassing from areas of former high use may provide an important driving mechanism for continued “global cycling” of a range of semi-volatile organochlorine compounds.     

Runoff of pesticides from rice fields in the Ile de Camargue (Rhône river delta, France): field study and modeling

A field study on the runoff of pesticides was conducted during the cultivation period in 2004 on a hydraulically isolated rice farm of 120 ha surface with one central water outlet. Four pesticides were studied: Alphamethrin, MCPA, Oxadiazon, and Pretilachlor. Alphamethrin concentrations in runoff never exceeded 0.001 microg L(-1). The three other pesticides were found in concentrations between 5.2 and 28.2 microg L(-1) in the runoff water shortly after the application and decreased thereafter. The data for MCPA compared reasonably well with predictions by an analytical runoff model, accounting for volatilization, degradation, leaching to groundwater, and sorption to soil. The runoff model estimated that runoff accounted for as much as 18-42% of mass loss for MCPA. Less runoff is observed and predicted for Oxadiazon and Pretilachlor. It was concluded that runoff from rice paddies carries important loads of dissolved pesticides to the wetlands in the Ile de Camargue, and that the model can be used to predict this runoff.     

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.     

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.

     

Pesticide contamination of ground water in the United States--a review

Over 70 pesticides have been detected in ground water. Aldicarb and atrazine along with the soil fumigants EDB and DCP and DBCP have been the pesticides most frequently detected in ground water. Atrazine concentrations have been correlated with high nitrate concentrations. The triazine herbicides, simazine and cyanazine, have also been detected in ground water. The annual amount of recharge, soil type, depth of aquifer from the surface, nitrate contamination and soil pH are important field parameters in determining ground-water contamination potential by pesticides. Pesticide leaching is reduced by proper choice of crop rotation, increasing pesticide application efficiency, and integrated pest management.     

Adsorption of organic vapors on polar surfaces- Recent advances

This paper summarizes recent research on the adsorption of organic vapors on surfaces. Since the low gas phase concentration range is typical for environmental situations, this review is restricted to these adsorption coefficients. Two environmental parameters have a strong influence on the adsorption of organic vapors on polar surfaces:temperature andrelative humidity (which is the most suitable parameter for describing the influence of ambient moisture). An exponential relationship was found for the adsorption coefficientversus relative humidity and the reciprocal temperature, respectively. Comparing the heats of adsorption, two different groups of substances emerged: polar chemicals exhibited heats of sorption which were higher than their corresponding heats of condensation due to their ability to form hydrogen bonds, while for the nonpolar compounds the opposite was true. Sorption takes place on the surface of an adsorbed water film when the relative humidity exceeds the value which is necessary to form a monomolecular layer of water on the surface of the adsorbent (≥ 30 % relative humidity). Therefore, at temperature below 0 °C, a change in the adsorption behavior might be expected due to a change of properties of the adsorbed water film. However, no alterations were observed at temperatures from -12 °C to + 4 °C (adsorption on quartz sand). The results were comparable to those at much higher temperatures (50 – 80 °C). A statistical approach for the prediction of the adsorption coefficients from physico-chemical parameters of the substances (vapor pressure, polarizability, and electron-donating capability) was developed and good agreement was found with experimental results and independent data from the literature. Finally, two special cases, the adsorption on bulk water and ice, are discussed.     

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.     

A comparison of predicted and measured levels of runoff-related pesticide concentrations in small lowland streams on a landscape level

Short-term pollution events via runoff are typical of streams in agricultural areas. Existing runoff models that simulate pesticide loss from agricultural fields require extensive input of information. There is thus a need for a simple model that can predict runoff-related pesticide concentrations in many streams on a landscape level when only limited data are available. To validate such a model, the runoff-related pesticide load of 18 small lowland streams was predicted with an extended version of the model "simplified formula for indirect loadings caused by runoff" (available from the Organisation for Economic Cooperation and Development, OECD). The authors suggest that the model presented here is suitable for use in routine exposure assessment of pesticides on a landscape level, as all input data (soil, slope, precipitation, pesticide application) are readily available from public authorities or could be generated by simple regional flood hydrograph curves. The predicted concentrations were compared with measured concentrations obtained by runoff-triggered sampling. Fungicides, insecticides and herbicides were detected in 17 streams, with max. concentrations measuring up to 29.7 microg/l for the fungicide azoxystrobin and 0.3 microg/l for the insecticide parathion-ethyl. Herbicides were detected in 16 streams, with max. concentrations between 13.7 and 1.2 microg/l. The linear regression between the predicted and measured concentrations (log-values) shows significant correlations for the following pesticides: azoxystrobin: r2=0.43; p=0.03; epoxiconazole: r2=0.71; por=0.5 microg/l).     

Evaluation of FOCUS surface water pesticide concentration predictions and risk assessment of field-measured pesticide mixtures—a crop-based approach under Mediterranean conditions

FOCUS models are used in the European regulatory risk assessment (RA) to predict individual pesticide concentrations in edge-of-field surface waters. The scenarios used in higher tier FOCUS simulations were mainly based on Central/North European, and work is needed to underpin the validity of simulated exposure profiles for Mediterranean agroecosystems. In addition, the RA of chemicals are traditionally evaluated on the basis of single substances although freshwater life is generally exposed to a multitude of pesticides. In the present study, we monitored 19 pesticides in surface waters of five locations in the Portuguese ‘Lezíria do Tejo’ agricultural area. FOCUS step 3 simulations were performed for the South European scenarios to estimate predicted environmental concentrations (PECs). We verified that 44% of the PECs underestimated the measured environmental concentrations (MEC) of the pesticides, showing a non-compliance with the field data. Risk was assessed by comparing the environmental quality standards (EQS) and regulatory acceptable concentrations with their respective MECs. Risk of mixtures was demonstrated in 100% of the samples with insecticides accounting for 60% of the total risk identified. The overall link between the RA and the actual situation in the field must be considerably strengthened, and field studies on pesticide exposure and effects should be carried out to assist the improvement of predictive approaches used for regulatory purposes.