Perspectives of a large scale environmental survey for chlorinated dioiins: water analyses

During 1983 and 1984, The Dow Chemical Company conducted a study to determine the extent of dioxin contamination at its Midland, Michigan plant and the surrounding area. The primary objectives of this study were to identify, rank order, and when possible quantify potential sources of dioxins to the environment and also to determine the extent of contamination in areas affected by the Dow facility. Early in the study, it was estimated that approximately 0.6g/year of 2378-TCDD was being emitted in 2.5 × 10¹⁰L of wastewater effluent. Data will describe observed sources of TCDD (both current and historical), environmental levels, existing water treatment methods, control measures taken, and future improvements on the water system to reduce TCDD in the effluent.     

Distribution of mono- through hexa-chlorobenzenes in floodplain soils and sediments of the Tittabawassee and Saginaw Rivers,Michigan

Introduction  

Chlorobenzenes are used as solvents or as feedstocks in the production of pesticide formulations, dyes, room deodorizers, moth-proofing agents, and de-inking solvents. Chlorobenzenes were produced by the Dow Chemical Company in Midland, Michigan, for several decades. In this study, concentrations of 12 chlorobenzene (CBz) congeners, from mono- to hexachlorobenzenes, were measured in more than 150 floodplain soil (FPS), surface sediment, and sediment core (SC) samples collected during 2002–2004 from the Pine River, Tittabawassee River, Shiawassee River, Saginaw River, and Saginaw Bay, Michigan.     

Comparative analysis of the structure of carbon materials relevant in combustion

The determination of the structure of carbon materials is an analytical problem that join the research scientific communities involved in the chemical characterization of heavy fuel-derived products (heavy fuel oils, coal-derived fuels, shale oil, etc.) and of carbon materials (polycyclic aromatic compounds, tar, soot) produced in many combustion processes.

The knowledge of the structure of these “difficult” fuels and of the carbon materials produced by incomplete combustion is relevant to research for the best low-environmental impact operation of combustion systems; but an array of many analytical and spectroscopic tools are necessary, and often not sufficient, to attempt the characterization of such complex products and in particular to determine the distribution of molecular masses.

In this paper the size exclusion chromatography using N-methyl-pyrrolidinone as eluent has been applied for the characterization of different carbon materials starting from typical carbon species, commercially available like polyacenaphthylene, carbon black, naphthalene pitch up to combustion products like soot and soot extract collected in fuel-rich combustion systems. Two main fractions were detected, separated and molecular weights (MWs) determined by comparison with polystyrene standards: a first fraction consisted of particles with very large molecular masses (>100 000 u); a second fraction consisted of species in a relatively small MW range (200–600 u). The distribution of these fractions changes in dependence on the carbon sample characteristics.

Fluorescence spectroscopy applied on the fractions separated by size-exclusion chromatography has been used and comparatively interpreted giving indications on the differences and similarities in chemical structure of such different materials.     

The use of bioluminescent biotests for study of natural and laboratory aquatic ecosystems

A set of bioluminescent tests was developed to monitor water quality in natural and laboratory ecosystems. It consisted of four bioluminescent systems: luminous bacteria, coupled enzyme system NADH:FMN-oxidoreductase-luciferase and triplet enzyme systems with alcohol dehydrogenase and trypsin. The set of biotests was applied for a small forest pond (Siberia, Russia), laboratory microecosystems polluted with benzoquinone and a batch culture of blue-green algae. Thereby effects of natural water compared to those of models of heavy pollution and “bloom” of blue-greens on the bioluminescent tests were revealed. The set of biotests was not affected by a natural seasonal variability of water quality in the unpolluted pond, but responded to the heavy pollution and the “bloom” of blue-greens. The set of biotests could be recommended as the alarm test to control the acute toxicity of natural water bodies.     

Fluorescence-based evidence for adsorptive binding of pyrene to effluent dissolved organic matter

Using fluorescence intensity measurements, pyrene interactions with different types of effluent dissolved organic matter (EDOM) originated from treated municipal wastewater are examined. Multiple observations show that fluorescence intensity of pyrene–EDOM solutions is non-linearly related to pyrene concentration, with distinct concave-up dependence. Testing the effect of pyrene concentration on fluorescence intensity of pyrene–EDOM solutions provides a tool to examine whether binding of an organic compound to EDOM follows linear or non-linear isotherm. Possible coupling between static and dynamic quenching effects was addressed while analyzing fluorescence data. Limited number of EDOM binding sites results in a non-linear binding isotherm such that the concept of pyrene “partitioning” between aqueous phase and “bulky” EDOM organic phase is hardly relevant. Maximal EDOM capacity for pyrene binding is estimated approximately as 0.1% w w⁻¹. Examination of the differences between the total fluorescence intensity of pyrene–EDOM solution and the fluorescence intensities of separated constituents (pyrene and EDOM) was used to illustrate the accumulation of pyrene–EDOM complexes and saturation of some EDOM binding sites. Strong interactions between pyrene and EDOM binding sites may result in pyrene distribution coefficients differing at least by a factor 3.5–7 at varying pyrene concentrations.     

Recycling of flame retardants containing printed circuits: A study of the possible formation of polyhalogenated dibenzodioxins/-furans

The generation of halogenated dibenzo-p-dioxins/-furans could be expected during recycling of printed circuits containing flame retardants. The presence of precursor substances (e.g. flame retardants like tetrabromobis-phenol A or PCB), partly elevated temperatures, and catalytical effects of copper seem to represent typical formation conditions for “dioxins”. To control the possible contamination of granulated material and thus of work places, in a pilot plant a test run was carried out with a hammer mill and an impact grinder. The air samples examined did not contain PXDD/F residues and the shredded material was contaminated only with PBDD/F at very low concentrations (0.03 – 1.13 ng/g). A test with printed circuits under thermal stress up to 300 °C in an oven generated low amounts of PBDD/F (0.74 – 4.51 ng/g). These tests provide proof that printed circuits can be recycled.     

Total mercury intake from fish and shellfish by Japanese people

Elevated mercury concentrations have been reported in fish in recent years. Japanese people eat a great deal of raw fishes and shellfishes as “Sashimi” and “Sushi”. The action level of large predatory fish such as tuna with total mercury levels exceeding the Japanese maximum permitted limit of 0.4 ppm is exempted from regulation in Japan. Therefore, current total mercury intake from fish and shellfish of Japanese people is unknown. The purpose of this investigation was to estimate the total mercury intake from fish and shellfish. It was found that the mean total mercury concentration of 1.11 ppm in tuna of eatable base as Sashimi or Sushi was clearly higher than the normal level. The mean total mercury intake from fish and shellfish was 0.17mg per capita per week . According to the hypothesis that 75% of total mercury in fish and shellfish is methylmercury, the weekly intake of 0.13 mg as methylmercury was corresponding amount to about 74% of provisional tolerable weekly intake 0.17 mg of methylmercury set by the Welfare Ministry of Japan.     

Registering and analysing data on detection of chemicals in the environment

As part of the research project “information system for environmental chemicals” a factual databank on a testset of 68 chemicals was developed. The set-up of the databank is described and the analysis of the results is shown for benzo(k)fluoranthene using a graphical boxplot illustration.     

Comparison of various sampling methods for PCDDs and PCDFs in stack gas

There have been discussions about how complete PCDDs and PCDFs are sampled from stack gas of waste combustion plants by various sampling methods. In Germany, at present, a sampling method is used, which was first proposed by Nottrodt et al.¹, consisting of a filter device, condenser, and an absorption train. Since this sampling procedure complicates sampling and analysis, we compared this “standard procedure” with a “dilution method”, where only a filter, impregnated with paraffin, is used as trapping device, and also tested the effectiveness of XAD-2 as an adsorption trap.

As standard procedure the standard train was always used in parallel to other sampling methods. The results of four parallel sampling periods confirmed, that comparable results are obtained, when parallel sampling is carried out with the standard train.

The result of our investigation can be summarized as follows: The total emission of PCDDs and PCDFs determined by different sampling procedures varies only insignificantly. This means that sampling and analysis for PCDDs and PCDFs in stack gas could be simplified considerably.     

A comparison of mussels (Perna viridis) and semi-permeable membrane devices (SPMDs) for monitoring chlorinated trace organic contaminants in Hong Kong coastal waters.

A comparison of mussels (Perna viridis) and semi-permeable membrane devices (SPMDs) was carried out at five sites, representing a gradient of contaminant concentrations, in Hong Kong coastal waters. Mussels, originally collected from a “clean” location, were deployed along with SPMDs at each site for 30 days. Analyses for chlorinated pesticides and polychlorinated biphenyls (PCBs) indicated that SPMDs have potential as monitoring tools, and to some extent can overcome the problems associated with mussels, such as natural variability, differing age, sex, and physical condition. However, in most cases, SPMDs failed to rank the sites in the same order as mussels in terms of contaminant concentrations. Nonetheless, in localities where mussels cannot survive – as shown at Kwun Tong in the present experiment – SPMDs may be valuable in providing an indication of potentially bio-available lipophilic pollutants.     

Lead and cadmium biosorption by extracellular polymeric substances (EPS) extracted from activated sludges: pH-sorption edge tests and mathematical equilibrium modelling

The sorption of Cd and Pb by extracellular polymeric substances (EPS) extracted from activated sludges originated from wastewater treatment plants (WWTPs) or Lab-scale bioreactors was investigated as a function of pH. The study was carried out using a polarographic method in the SMDE (stripping mercury dropping electrode) mode which is suited to determine labile metals in solution containing soluble ligands such as EPS. The results obtained provide evidence of the presence of a pH-sorption/desorption edge for Cd and Pb by EPS. The use of Kurbatov’s model gives information on the mechanisms involved through the determination of “relative complexation constants” (operationally defined) and the number of protons exchanged. The use of this model demonstrates that proton exchange with metals is not the only mechanism involved in metal biosorption by EPS. Other mechanisms such as cation exchange with Ca or Mg, global electric field surrounding the ligand or micro-precipitation of metals could be involved in metal sorption by EPS. The position of the pH-sorption edge curves and the “relative complexation constants” show that Pb displays a greater affinity for EPS than Cd. The studied EPS have large differences regarding binding strength of Cd and Pb. These differences are not correlated with the organic parameters measured to characterize the EPS, however the mineral fraction of the EPS could be involved to a large extent in the sorption of metal.     

Qualitative and quantitative cancer risk assessment of 2, 3, 7, 8-tetrachloro-dibenzo-p-dioxin (2, 3, 7, 8-TCDD)

The carcinogenicity of 2,3,7,8-TCDD at multiple organ sites in animals has been well established by several cancer bioassays. Results of two of the most notable of these, the Kociba et al. (1978) rat feeding study and the National Toxicology Program (1980) gavage study in rats and mice showed hepatocellular carcinomas in two strains of female rats and male and female mice. Other tumor sites included carcinomas of the lung, tongue, hard palate and nasal turbinates, thyroid, and subcutaneous tissue. The evidence for carcinogenicity of 2,3,7,8-TCDD in animals is regarded as “sufficient” using the classification system of the International Agency for Research on Cancer (IARC).

Two Swedish epidemiologic case-control studies (Hardell and Sandstrom, 1979; Eriksson et al. 1979, 1981) reported a significant five- to sevenfold excess risk of soft-tissue sarcomas (STS) from occupational exposure to chlorinated phenoxyacetic acid herbicides and/or chlorophenols. Additionally, several small cohort studies collectively exhibited an unusual cluster of STS, significantly increased over combined expected incidence. Problems with these studies do not appear to be sufficient to discount this excess risk. The human evidence alone for the carcinogenicity of 2,3,7,8-TCDD is “inadequate” using the IARC classification. However, for 2,3,7,8-TCDD in combination with chlorinated phenoxyacetic acid herbicides and/or chlorophenols, the human evidence is considered to be “limited.” The overall evidence for carcinogenicity considering both animal and human studies would place 2,3,7,8-TCDD alone in the IARC category 2B, meaning that the substance is probably carcinogenic in humans. The overall weight of evidence for 2,3,7,8-TCDD in combination with chlorinated phenoxyacetic acid herbicides and/or chlorophenols is regarded as IARC category 2A, also meaning that they are probably carcinogenic for humans.

Using current EPA methodology for quantitatively estimating cancer risks, several animal data sets have been analyzed. Comparing the results, the upper-limit incremental unit risk estimate is 1.6 × 10⁻² for a lifetime exposure of 1 ng/kg/day. This estimate is derived from a lifetime feeding study (Kociba et al., 1978) in which 2,3,7,8-TCDD induced tumors of the liver, lungs, hard palate, and nasal turbinates in female rats. Incremental unit cancer risks are also extrapolated for lifetime 2,3,7,8-TCDD exposures in water and air. Based on continuous lifetime exposure to 1 ng/L 2,3,7,8-TCDD in drinking water, the upper-limit estimate of extra cancer risk per individual is 4.5 × 10⁻³. For lifetime exposure to 1 pg 2,3,7,8-TCDD/m³ in the ambient air, the upper-limit individual risk is 3.3 × 10⁻⁵.     

Changes in polycyclic aromatic hydrocarbon content of atmospheric particulate monitored using fuzzified chromatograms

A simple rapid chromatographic technique for polycyclic aromatic hydrocarbons which is poor at speciation has been used to obtain data on the presence of the class in air particulate. Matching of such chromatograms to a fuzzified reference from these data is illustrated as a practical way to obtain overviews of changes in species distributions summarized in few values. Such information is lost in more commonly used surrogate approaches to “class analyses”.     

Toxicity tests with luminescent photobacteria and quantitative structure activity relationships for nitroparaffins

EC₅₀ values of different nitroparaffins were determined by a photobacterium phosphoreum toxicity test. Octanol/water partition coefficients were determined by a reversed phase HPLC method. From these experimental data quantitative structure activity relationships were deduced which point to a dependence of toxicity on a “form factor” that includes the number of methyl and methylene groups in a molecule. The hypothesis will be formulated that the specific effects depend on the number of methylgroups and an equation for specific effects is given.     

Utilization and degradation of imazaquin by a naturally occurring isolate of Arthrobacter crystallopoietes

A species of bacteria that is capable of utilizing imazaquin as the sole carbon source was isolated from soil with repeated imazaquin applications, and was identified as Arthrobacter crystallopoietes (designated as strain “WWX-1”). This isolate degrades imazaquin as high as 200 μg ml⁻¹, and the estimated dissipation half-lives increased from 1.51 d for the treatment at 50 μg ml⁻¹ to 4.75 d for 200 μg ml⁻¹. Optimal growth of WWX-1 in mineral salt medium with 50 μg ml⁻¹ imazaquin was obtained at 35 °C and a pH of 5.0. Growth of WWX-1 was also observed in mineral salt medium with the addition of other imidazolinone herbicides such as imazethapyr and imazapyr, but not with different classes of herbicides such as metsulfuron-methyl. Two imazaquin metabolites were detected, and spectral analysis with HPLC–MS, ¹H NMR, and IR revealed one metabolite with a molecular weight (MW) of 199 as quinoline-2,3-dicarboxylic anhydride. We propose that A. crystallopoietes (WWX-1) could serve as an efficient biodegradation system for remediation of water and soils that are heavily contaminated with imazaquin or other structurally similar chemicals.     

Formation of PCDDs and PCDFs by the chlorination of water

Two samples of tab water and double distilled water were chlorinated using chlorine gas. A series of PCDFs could be identified from these experiments, however no PCDDs could be found. The two water samples gave very similar isomeric patterns ( . . tetra-CDFs), however the congener profile (Cl₄ --- Cl₈) was different. These experiments indicate that all products formed by chlorination reactions are potentially contaminated by PCDFs by a specific “chlorine pattern”.     

Photomineralization of n-alkanoic acids in aqueous solution by photocatalytic membranes. Influence of trialkyl vanadates as catalytic promoters of immobilized titanium dioxide

The Ti0₂-mediated photomineralization of 8–1000 ppm of methanoic acid, of 6–100 ppm of ethanoic acid, of 6–180 ppm of propanoic acid, and of 6–90 ppm of n-decanoic acid in aqueous solutions was studied at 296± 2 K or 308 ± 2 K, with low and high pressure mercury arc lamps (radiant power in the absorption range 8 and 145 W respectively), using PHOTOPERM® CPP/313 membranes containing immobilized 30±3 wt.% Ti0₂, and, in parallel runs, 7 wt.% of a synergic mixture of tri(t-butyl)- and tri-(i-propyl) vanadate(V) as photocatalytic promoter. Stoichiometric H₂0₂ was used or, in some of the runs, 0₃, at saturation, as oxygen suppliers. Disappearance of total organic carbon (TOC) was followed as a function of time. To fit kinetic curves up to complete photomineralization, a kinetic model was employed, already used successfully in previous studies, which considers appearance and disappearance of all intermediates, as if they were represented by a hypothetical single molecule, mediating all of them. The photocatalytic activity of trialkyl vanadates was evaluated from quantum yields at “infinite” concentration, with respect to the maximum allowable efficiencies. When using O₃, a dark catalysis effect clearly appeared towards intermediate species produced during the photocatalysed degradation.     

Study of the chemistry of an acid soil column and of the corresponding leachates after the addition of an anaerobic municipal sludge

A column leaching study was carried out over a period of 77 days to determine the changes in the chemistry of an acid soil and of the corresponding leachates after the addition of an anaerobic sludge (equivalent to 69 Mg DW ha⁻¹). By the end of the experiment, the addition of the sludge to the soil had induced an increase in soil pH (from pH 3.6–4.0 to pH 4.1–4.8), in spite of the pronounced decrease in pH detected in the leachates by day 18 of the experiment. The decrease in pH (down to pH 3.3) occurred at the same time as leachate SO₄ and Fe peaked. Once the acidification attributed to sulphide oxidation ceased, the “liming effect” of the sludge became evident and counteracted further proton production – such as that associated with oxidation of NH₄ – at least for the duration of the study. Concentrations of Zn, Cd, Ni, and to a lesser extent, Pb in leachates displayed pulses at the beginning of the experiment (first 12 days), whereas the concentration of Cu followed a more irregular pattern; the concentrations of these metals never surpassed the European threshold values for drinking water. In contrast, concentrations of NO₃, Mn, and Cr in leachates had increased by the end of the experiment – in parallel with an increase in dissolved organic C (DOC) – and surpassed the European threshold for drinking water. Mineralisation of native soil organic C (SOC) was enhanced by the addition of this N-rich residue, and the organic C mass balance at the end of the experiment was negative. Nitrogen mass balance, although positive, exhibited a loss of 77% of the N added to the system. The results obtained indicate that application of this sewage sludge to a soil with a pH < 5, at the loading rate used here, and without liming (i.e., non fulfilment of the requirements of the present European Directive) may pose a risk in terms of groundwater contamination.     

Distribution of endocrine disruptors in the Llobregat River basin (Catalonia, NE Spain)

The Llobregat basin is a Mediterranean fluvial system with major agricultural, urban and industrial impacts. We combined chemical quantification by liquid chromatography–mass spectrometry with electrospray interface (LC-ESI-MS) and the recombinant yeast assay (RYA) assays to estimate the loads of endocrine disrupting compounds (EDCs) along the basin. Chemical analysis revealed maximum concentrations (at μg l⁻¹ level) of alkylphenols at the lower course of the Llobregat River, which correlated with high levels of estrogenic activity detected by RYA. Analysis by RYA and LC-ESI-MS of influent and effluent waters from four sewage treatment plants (STP) discharging into the basin showed the removal of 80–95% of EDCs by STP treatment. Chemical analysis data and RYA data showed a quasi-linear correlation, demonstrating the complementariness of both methods. Our data suggest that the concentrations of the analysed compounds were enough to explain the total estrogenicity of water and STP samples from the Llobregat basin.     

Environmental risk assessment for trisodium [S,S]-ethylene diamine disuccinate, a biodegradable chelator used in detergent applications

Environmental safety data are presented for [S,S]-Ethylene Diamine Disuccinate ([S,S]EDDS), a new, biodegradable, strong transition metal chelator. An environmental risk assessment for its use in detergent applications, which takes into account the chelating properties of [S,S]-EDDS, is proposed.

A property of [S,S]-EDDS that distinguishes it from other strong transition metal chelators is its, “ready” and transparent (no recalcitrant metabolites) biodegradation profile. Because its sorption to activated sludge solids is low ( Kp of 40 1/kg), removal of [S,S]EDDS during sewage treatment, which is greater than 96% as determined by the Continuous Activated Sludge test , is mainly ascribed to biodegradation. At projected use volumes in detergent applications [S,S] - EDDS predicted steady-state concentration in rivers leaving the mixing zone will be below 5 pg/I due to rapid biodegradation. [S,S]-EDDS exhibits low toxicity to fish and Daphnia ( both EC₅₀s> 1000 mg/l). By contrast, due to limitation of the algal test for chelators apparent toxicity was observed (EC₅₀ = 0.290 mg/l, NOEC - No observable Effect Concentration = 0.125 mg/l). Schowanek et al. [1] demonstrated that this is not toxicity sensu stricto but a chelation effect of trace metals in the test medium and of resulting essential nutrients limitation. This requires specific attention when the results of algal toxicity are to be extrapolated to a field situation to perform realistic risk assessment. Metal speciation calculations, using MINEQL+, show that at the predicted environmental concentrations of [S,S] - EDDS (1–5 μg/l), such a chelation effect would be insignificant. These calculations allow to estimate the NOEC for chelation effects in the field to be in the range of 0.250-0.500 mg/l, depending on the background water chemistry. These values are well above the laboratory NOEC.

An environmental risk assessment was performed using the EUSES (1.0) program. EUSES is currently the EU recommended tool for conducting risk assessments (TGD 1995). It was applied to estimate the river water and soil concentrations from production, formulation and private use life stages. The estimated PEC/PNEC ratio in all relevant environmental compartments is smaller than 1, indicating “no immediate concern” at the anticipated usage level.