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The development of microfluidic sensors as cost-effective strategies for environmental monitoring has been a primary goal for the platform since the 1980s. This paper outlines the lessons learned, during the designing and testing of biochemical assay protocols on a Lab-on-a-Disc (LOAD), using "MARIne environmental in-situ Assessment and monitoring tool BOX" (MARIABOX) project. Two novel platforms were produced in the MARIABOX project, with the latter mostly falling outside the scope of this study: A centrifugal microfluidic platform which would perform on-disc biochemical assays, and a deployable ‘Smart Buoy’ which would manage the storage, performance and biosensor detection of the centrifugal microfluidic platform. The technical challenge of the project was an -in-situ system and the monitoring of eight separate analytes including microcystin, saxitoxin, domoic acid, azaspiracid, perfluorooctanesulfonic acid, naphthalene, camphechlor and heavy metal presence. This paper highlights the concurrent and collaborative strategy used by the 14 international partners of the MARIABOX project, required to achieve the 4-year development target.

Research examined solubility of toxaphene by partially miscible organic solvents (PMOSs) in water solutions. Longer-chain and straight-chain alcohols displayed greater toxaphene cosolvency in cosolvent-water solutions than their shorter and branched counterparts. Higher molecular weight PMOSs formed ternary systems that enhanced solubility of toxaphene beyond lone completely miscible organic solvents (CMOSs). An effective first-order bi-continuum model was developed to simulate non-equilibrium sorption in miscible displacement of toxaphene from soil with varied cosolvent solutions. Overall, results showed that cosolvents increase solubility and removal efficiency of toxaphene from soil; which may be applicable for improved cosolvency and remediation of other complex chlorinated organics.

Growth, Stress Response, and Selected Physiological Parameters in Juvenile Arctic Charr, (Salvelinus alpinus) C. A. Blanar,* M. A. Curtis, H. M. Chan 1 Department of Natural Resource Sciences, Macdonald Campus, McGill University, Ste. Anne de Bellevue, Quebec, Canada 2 School of Dietetics and Human Nutrition and Centre for Indigenous Peoples’ Nutrition and Environment (CINE), Macdonald Campus, McGill University, 21, 111 Lakeshore Road, Ste. Anne de Bellevue, Quebec H9X 3V9, Canada

Twenty-seven black guillemot eggs and 39 livers were analysed for polychlorinated biphenyls (PCBs), chlorinated pesticides including chlordane-related compounds and toxaphene, and polybrominated diphenylethers (PBDEs). The samples were collected at Qeqertarsuaq (Godhavn, West Greenland) and Ittoqqortoormiit (Scoresbysund, East Greenland). The concentrations of halogenated organic compounds in samples from East Greenland were somewhat higher than the corresponding concentrations from West Greenland. Differences in compound patterns were found between West and East Greenland, with higher percentages of the heavier PCB molecules, p,p(')-DDE and alpha-HCH in the samples from Ittoqqortoormiit. Similarly, different levels and different compositions were observed for eggs and livers. The eggs had generally higher concentrations of all compounds as well as higher percentages of CHB-50, CHB-62 and alpha-HCH than liver samples from the same area. Dividing the liver samples into age groups revealed increasing concentrations with age.

Toxaphene was used extensively as an insecticide on cotton in the southern United States until its use was restricted in 1982. Toxaphene has been found in the water and fishes from the Great Lakes, and several authors have qualitatively linked this observation to atmospheric transport from the southern United States, although no detailed field study has been done to confirm this suggestion. We implemented a sampling network to measure the gas-phase concentrations of toxaphene near Lake Michigan at Sleeping Bear Dunes, MI; Bloomington, IN; Lubbock, TX; and Rohwer, AR. The toxaphene concentrations referenced to 288 K were 11 +/- 1, 25 +/- 1, 160 +/- 3, and 950 +/- 30 pg/ m3, respectively. We combined these concentration data with a nonparametric, backward trajectory, multiple regression model of the following form: ln(P) = a0 + a1/T + a2theta where P is the partial pressure of toxaphene (in atm) in a given sample, T is the atmospheric temperature at the sampling site during sampling (in degrees Kelvin), and theta is 0 if the backward trajectory comes from the north and 1 if the trajectory comes from the south. The parameters of this model were generally significant, giving a temperature coefficient (a1) corresponding to 45 +/- 8 kJ/mol and a positive directional coefficient (a2) of 0.6 +/- 0.2 (except for Texas, which was not significant). The positive sign and magnitude of the directional coefficient indicates that the sources of toxaphene are located south of the sampling sites. We also compared the chemical behavior of toxaphene in the atmosphere and found that the congener ratios were similar at the different sampling sites but slightly different from various toxaphene standards.

Toxaphene, as a general-purpose insecticide, was widely used in the United States. The use of toxaphene in the United States can be divided into four different periods between 1947 and 1986, with total usage of about 490 kt, and total production around 720 kt. Inventories of gridded usage of toxaphene in the United States with 1/6° by 1/4° latitude/longitude resolution have been created by using different gridded cropland and cattle as surrogate data. The intensive use of toxaphene on croplands was concentrated in the southeastern part of the United States with the highest usage of 2 kt per grid cell. The results show that the state of Alabama was the largest user of toxaphene, reaching as much as 87 kt, followed by Mississippi at 60 kt. The total usage in the top 10 states is 410 kt, 84% of the national usage in the United States. The use in the first six states, Alabama, Mississippi, Georgia, Arkansas, Texas, and South Carolina, is 350 kt, 71% of the national usage in the United States.

In the United States, it is necessary to analyze for toxaphene using approved, validated methods acceptable to the regulatory agencies. As a result of an interlaboratory study and technical exchanges among the US EPA Region IV (EPA), the State of Georgia Environmental Protection Division (EPD), and Hercules Incorporated, guidelines for the application of SW-846 Method 8080 were developed. Results of analyses for sludge, soil, and water samples agreed within a percent relative standard deviation (% RSD) range of 6.9-20%. Through continued technical interchanges, guidance for the application of SW-846 Method 8081 has been developed. The results of analyses of fourteen split samples of soil and sediment produced a percent relative standard deviation that ranged from 1.6% to 127%, with an average of 38%. When two unusually divergent results were removed from consideration, the average % RSD reduced to 26%. The results of analyses of split samples show agreement between the EPA laboratory and a Hercules contract laboratory. Therefore, the guidance has achieved its purpose of producing agreement among data from different laboratories so that data reviewers may have assurance that the analytical method has been applied correctly and consistently for the determination of toxaphene in environmental samples.

The unsaturated C10-components and their amounts in technical toxaphene have been characterized with the help of column chromatography/FTIR spectroscopy using the typical absorption bands of the >C...

Toxaphene is a complex mixture of at least 600 hexa- to decachlorinated bornanes and bornenes, which was used as an insecticide in the United States from the late 1950s to the mid-1980s. A previous study in our laboratory showed that the levels of toxaphene in lake trout collected in 1982 and 1992 from Lake Superior had remained about the same but that the concentrations in lake trout from the other Great Lakes had decreased during this same time period. These observations in Lake Superior trout were counter-intuitive given that toxaphene had been banned in 1982. We have reinvestigated this issue using more samples from both Lake Superior and northern Lake Michigan and using an improved analytical method. The level of toxaphene was constant in all of the trout samples from Lake Superior during the period 1977−1992, while the level decreased by a factor of 1.4−5 in trout from the other Great Lakes. These results suggest that the toxaphene concentrations in very large and very cold lakes (such as Lake Super...

Two interlaboratory studies on individual toxaphene congeners have been organised by the project Quality Assurance of Information for Marine Environmental Monitoring in Europe (QUASIMEME). Fifteen laboratories analysed two standard solutions in the first study and 13 laboratories analysed a standard solution and two cleaned biota extracts in the second study. The coefficients of variation obtained for the standard solutions were 6-21% and for the cleaned extracts 16-39%. Although the results were comparable to those of other studies, further improvement in the level of agreement between the participating laboratories was considered possible. (C) 2000 Elsevier Science Ltd.

By definition, persistent organic pollutants (POPs) persist in the environment, bioaccumulate through the food chain, and may cause adverse effects to human health and the environment. Although their production and use have been banned or severely restricted in many countries, accidental contamination of the food chain with POPs may occur even in countries where strict surveillance systems have been implemented, and these rare events usually hit the headlines of the press and give rise to concern and increased awareness of the general public. Due to the lipophilicity of POPs they accumulate in the fat phase of foodstuffs and are therefore of interest not only for environmental and public health scientists, but also for the lipid chemist. Reports on occurrence and levels of POPs in the food chain appear regularly in major food chemistry journals. The aim of this dossier is to bring new developments regarding regulatory, toxicological, and analytical aspects as well as the behaviour of POPs in the environment to the attention of lipid scientists. In particular, those mechanisms governing the ubiquitous distribution of POPs and the concomitantly observed background contamination of foodstuffs should be of interest to those involved in the routine monitoring of food safety. Progress has been made to understand better the toxicities of individual congeners, and it is important to expand this knowledge base as a proper foundation for risk assessment. Safeguard measures to reduce POP burden are already in place in many countries, but a joint effort is needed to minimise world-wide exposure to POPs. At this point, the Editors of the Journal would like to express their gratitude to the authors for their valuable contributions to this dossier.

Organochlorines (DDT, toxaphene, PCBs, chlordane, HCHs, dieldrin) were quantified in the blubber of eleven fur seals of the species Arctocephalus pusillus pusillus. The sample clean-up included microwave-assisted extraction (MAE), gel-permeation chromatography (GPC), adsorption chromatography on silica gel and quantitation with GC/ECD. Compounds of technical toxaphene (CTTs) were determined after separation from the PCBs. Highest levels arose for p , p ′-DDE (7–1000 μg/kg). A so far unknown compound labelled Q1 caused the second most abundant peak in the samples. Q1 was identified as a heptachloro compound by GC/MS in the electron capture negative ionisation and electron impact ionisation mode. Levels of Q1 were estimated relative to the ECD response factor of trans -nonachlor. These estimated Q1 levels ranged from 27 to 351 μg/kg being in the range or higher than the levels of PCBs (6–697 μg/kg), toxaphene (10–97 μg/kg), chlordane (3–159 μg/kg), and dieldrin (4–36 μg/kg). One sample which showed significantly higher DDT and PCB levels (but not toxaphene, dieldrin, Q1, and chlordane) than the others is most likely migrated from an area higher polluted with DDT and PCBs. Another one showed very low levels which were not explained. Except these samples, the levels determined in the blubber were among the lower levels reported for this kind of tissue. The data also confirmed that the organochlorine levels in Africa are varying from region to region, and that there is still a need for further research.

The insecticide toxaphene, a complex mixture of several hundred components, is readily degraded in the environment. Only very few hepta-, octa-, and nonachlorobornanes are accumulated in higher organisms. Of the 2626 isomers that are theoretically possible, only 2-endo,3-exo,5-endo,6-exo,8,8,9,10,10-nonachlorobornane (B9-1679) is abundant in marine mammals. Using molecular models, we found that the nine bulky chlorine substituents of B9-1679 occupy conformations on the bornane backbone that result in a molecule that is free of steric hindrance and ring strain. The thermodynamic data derived from our modeling efforts proved to be predictive of the persistency of B9-1679 and 13 other hepta-, octa-, and nonachlorobornanes in mammals.

Enantioseparations of 26 chiral organochlorine compounds (α-hexachlorocyclohexane, toxaphene, chlordane, atropisomeric polychlorinated biphenyls) were studied with GC–electron-capture detection. The chiral stationary phases (CSPs) consisted of 35% heptakis (6 -O-tert. -butyldimethylsilyl-2,3-di -O- methyl)-β-cyclodextrin (β-TBDM) diluted in OV1701. One CSP was made of pure β-TBDM (purity>99%) while the other was randomly silylated β-TBDM. High-temperature gas chromatography showed that this CSP contained five products in almost equal amounts. Both β-TBDM columns were installed in parallel in the same GC system. On the randomly silylated β-TBDM, aromatic compounds had shorter and aliphatic compounds had longer retention times than on the purified β-TBDM. The randomly silylated β-TBDM resolved the enantiomers of 24 compounds (16 of them were baseline separated) and the purified β-TBDM only six (four of them were baseline separated). Thus, the purification of β-TBDM decreased the efficiency of the chiral resolution of organochlorine compounds on β-TBDM. The results clearly demonstrate that the randomly silylated β-TBDM contains one or more side products more suitable for the enantioseparation of organochlorine compounds than the purified β-TBDM.

Testing of Heliothis armigera larvae by topical application during 1973-74 and 1974-75 showed high levels of resistance to DDT in strains from Brookstead (>100-fold), Bowen (>100-fold), St. George (97-fold) and Capella (66-fold). Lower levels of resistance were shown in strains from Mareeba (37-fold), Bundaberg (22-fold), Redland Bay (30-fold) and Cambooya (15-fold). The Capella and St. George strains were less susceptible to DDT + camphechlor than the Brookstead strain, but resistance to this insecticide mixture was not considered to have been proven. The St. George strain was 21 times more resistant to endosulfan than the Brookstead strain. No evidence of resistance to parathion-methyl was demonstrated. Two strains of H. punctigera showed no resistance to DDT.

The HRGC determination of toxaphene residues in environmental samples is often difficult because of different degradation rates and accumulation behavior of individual toxaphene components. Therefore, isolated environmentally relevant chlorinated bornanes are used as standards. During the last years, single components as well as different combinations of them have been tested for their suitability for HRGC-HRMS-ECNI quantification. In this study, Parlar #26, Parlar #40, Parlar #41, Parlar #44, Parlar #50, and Parlar #62 have been used. The results show the sum of these six components to be at least 80–85% of toxaphene in fish oils.

Fragestellung: Wie haben sich die Konzentrationen der Chlorkohlenwasserstoffe (CKW) im Fettgewebe von Kindern wahrend der letzten 14 Jahre verhalten? Sind noch andere als die bisher bekannten Schadstoffe im Fett abgelagert? Methode: In Fettgewebsproben von 1267 Sauglingen, Kindern und Adoleszenten aus West- und Ostdeutschland sowie aus Saratow, Rusland, wurden die Konzentrationen der CKW mittels Gaschromatographie bzw. Massenspektrometrie quantitativ bestimmt und auf den Fettgehalt bezogen angegeben (µg/kg Fett=ppb). Ergebnisse: Die Konzentrationen der bisher bekannten CKW sind wahrend der letzten Jahre alle stark zuruckgegangen. Es wurden aber auch bisher unbekannte CKW im Fettgewebe entdeckt, namlich 2 Toxaphene (Parlar 26 und 50) in geringer Menge. Schlusfolgerung: Zwar ist die Belastung unserer Kinder mit den bisher bekannten CKW wahrend der letzten Jahre deutlich zuruckgegangen, doch fuhrten empfindlichere Nachweismethoden zum Nachweis bisher unbekannter potentieller Schadstoffe im Fettgewebe, so das eine vollige Entwarnung z.Z. noch nicht gerechtfertigt ist.

Sediment cores were analyzed for toxaphene from three of the Great Lakes (Superior, Michigan, and Ontario) and from two small control lakes near Lake Superior that receive inputs of toxaphene from only the atmosphere. The two cores from northern Lake Michigan had higher surface concentrations (33 ± 12 ng/g) than the southern Lake Michigan core and the remainder of the Great Lakes cores, which were similar (15 ± 4 ng/g), and similar to the surface concentration in one of the control lakes (9 ng/g). Evidence consistent with the slow degradation of toxaphene (t1/2 ≥ 50 yr) in some of the sediment cores was found. The similar concentrations among all the Great Lakes cores and the control lake core provide strong evidence that the dominant source of toxaphene to the Great Lakes is atmospheric input. The higher concentrations in the northern Lake Michigan cores indicate that northern Lake Michigan may be receiving about 30−50% of its current inputs from non-atmospheric sources. Lake Ontario and Lake Superior ma...

A major compound of technical toxaphene (CTT) was isolated from seal blubber. The structure of the octachlorobornane was elucidated by use of 1H-NMR and mass spectrometry. The isolate had the struc...

Capillaries based on tert.-butyldimethylsilylated β-cyclodextrin (TBDMS-CD) diluted in OV-1701 have gained increasing interest for the enantioselective separation of lipophilic polychlorinated pesticides. A modified test according to Schurig for chiral stationary phases was not suitable for testing TBDMS-CD due the lack of sufficiently lipophilic compounds. A test mixture was developed containing the chiral polychlorinated pesticides α-hexachlorocyclohexane, cis- and trans-chlordane, heptachlor-exo-epoxide and 2-exo,3-endo,5-exo,6-endo,8,8,9,10,10-nonachloro-bornane. They are especially sensitive to changes in the enantioselective properties of TBDMS-CD which is also frequently used for these compounds. Cis- and trans-chlordane with different enantiomer ratios facilitate the detection of changes of the enantiomer elution order. Test results of laboratory-made and commercial capillaries are presented showing the usefulness of the test to detect differences in the enantioselective behaviour such as changes in the elution order of enantiomers. Electrospray MS was used for the characterisation of TBDMS-CD. The analysed batches contained homologues with 7–10 TBDMS groups in a mixture of variable composition. This is assumed to be the reason for the observed differences.

Six pure polychlorinated bornanes isolated from technical toxaphene, namely, Parlar 32 (toxicant B), Parlar 42a (toxicant A1), Parlar 42b (toxicant A2), Parlar 49a, Parlar 56, and Parlar 59, as well as the technical mixture were investigated as to their fate in a loamy silt under anaerobic conditions by laboratory studies taking 4 or 6 months. All test substances shared the geminal dichloro group in the C-2 position and, additionally, one chlorine atom each in the C-5endo and C-6exo positions, respectively. Reductive dechlorination was the major reaction leading to a sequential removal of a chlorine atom from each geminal dichloro group. Generally, in the first step of transformation, all six compounds lost a chlorine atom from the geminal dichloro group in the C-2 position, preferentially from the endo-position. The dechlorination rate was in the order of nonachlorobornanes > octachlorobornanes > heptachlorobornanes. While the two monodechlorination products formed from Parlar 32 underwent no further tra...

An abundant heptachloro bornane in cod livers, TOX7, has been isolated by repeated high performance liquid chromatography. Its identity was confirmed by GC/MS in the EI and ECNI mode. Larger quantities of TOX7 were isolated from Melipax® and its structure was elucidated by EI mass spectrometry and 1 H-NMR measurements as 2-exo, 3-endo, 5-exo, 9, 9, 10, 10-heptachlorobornane. The structural similarity of TOX7 with TOX8 as well as Parlar #41 were discussed.

A summary is given of research conducted by our laboratory since 1991 on the dispersion and pathways of persistent organochlorines (POCs) to remote regions of the Northern North Atlantic. This review includes data not previously published and an overall interpretation of our results. Levels of polychlorinated dibenzo-p-dioxins, dibenzofurans, biphenyls and pesticides in marine mammals and sediments from these areas are presented and discussed. Special attention is given to the levels of polychlorinated bornanes (toxaphene), to date the most heavily used insecticide worldwide. Finally, temporal trends are presented.

In the literature the nomenclature used for chlorinated substances with bornane and camphene skeletons is nonuniform. In order to prevent misunderstandings the current WPAC rules are presented and applied to known Toxaphene components.

The historical input of toxaphene to Lake Ontario has been determined. We analyzed total toxaphene concentrations in eight Lake Ontario sediment cores by electron capture gas chromatographic mass spectrometry and found that toxaphene maximizes in 1973 ± 6 yr with a horizon date of 1945 ± 6 yr. The maximum toxaphene flux to Lake Ontario sediment was 22 ± 8 μg/m 2 yr in about 1973, and the total toxaphene load in the lake is 10 ± 3 t. By comparing the toxaphene burdens for the cores, we conclude that toxaphene is deposited to Lake Ontario sediment from both the Niagara River and from the atmosphere. We also found that toxaphene is slowly dechlorinated after deposition in Lake Ontario sediment.

A systematic code for a comprehensive numbering of toxaphene congeners on the basis of IUPAC rules has been developed. All chlorinated bornanes were characterized with a descriptor consisting of up to six letters and numbers. Each descriptor presents both enantiomers in the case of chiral compounds. Furthermore, chlorinated bornane congeners with a known structure are presented with both IUPAC nomenclature and the new systematic code. A computer program listing all the congener numbers is available from the authors.

Residues of DDT and its metabolites, hexachlorocyclohexanes (HCHs), chlordane, toxaphene, polychlorinated biphenyls (PCBs), and hexachlorobenzene (HCB) were determined by GC ECD and GC MS in the blubber of a seal (Phoca caspica) from the coast of Iran on the Caspian Sea. The organochlorine pattern was dominated by DDT and its metabolites while PCBs (65 PCB congeners including non-ortho PCBs were quantified) only played a minor role. The high content of β-HCH determined by GC ECD and confirmed by GC MS was interpreted to be caused by local sources. On the other hand, residues of chlordane compounds were correlated to atmospheric long-range transport.

Toxaphene (camphechlor) is a pesticide consisting primarily of chlorinated bornanes (CHBs) which was widely used until the mid 1980s. Toxaphene continues to be a major contaminant in marine and freshwater biota, with levels in marine fish exceeding some regulatory guideline limits. Methods of analysis for CHBs include gas chromatography with detection by electron-capture negative ion and electron ionization mass spectrometry, as well as electron-capture detection. Until recently quantification of toxaphene was limited by lack of suitable analytical standards and by limited information on the structural identity of CHB residues in environmental samples. This article reviews recent developments, such as the identification and synthesis of CHB congeners, and new information on spatial and temporal trends.

Theoretical aspects of polychlorinated bornanes—the major part of technical toxaphene—and the composition of technical toxaphene were compared with results derived from multidimensional gas chromatograph analysis of the multicomponent mixture. Stereochemical aspects and a common nomenclature for polychlorinated bornanes are presented. Considerations of the persistence of some toxaphene compounds are made.

There are still wide differences in the number of congeners estimated and measured for the insecticidal toxaphene mixture. Purely theoretical considerations are not very helpful, since compounds with the most unlikely Cl substitution are counted and included just like those that are known and already isolated. Counting the substances with the aid of a high resolution GC-MS system can, aside from the errors that are involved, not provide any structural information except whether the compounds are saturated or unsaturated. For this reason it is not known what chlorine substitutions are possible for the bornanes and accordingly which are present in the mixture. Recent results on the isolation and structural elucidation of 27 congeners form the basis for postulates made in this contribution concerning the structure of chlorinated bornanes and a calculation of the number of significant toxaphene components. This allows a concrete picture to be formed of this class of substance.

The structure of the two most abundant toxaphene congeners has unequivocally been established by 500 MHz1H NMR spectroscopy as 2-endo,3-exo,5-endo, 6-exo,8,8,9,10,10-nonachlorobornane (TOX9) and as 2-endo,3-exo,5-endo,6-exo,8,8,10,10-octachlorobornane (TOX8). Semiempirical calculations (AM1 and PM3-MNDO) were carried out for both structures. The distance information found by nuclear Overhauser enhancement (NOE) for the protons is in agreement with the energy minimized AM1 and PM3-MNDO structures. For these definitively established NMR data for TOX8 and TOX9, together with literature data for other toxaphene isolates, a set of rules has been derived for1H chemical shifts in polychlorinated bornane structures. A set of rules is also proposed for assigning systematical nomenclature to NMR-derived polychloro bornane structures.

The HRGC determination of Toxaphene R residues in fish tissues is often difficult because of the differing accumulation behaviour and decomposition rates of the individual Toxaphene compounds. This problem can satisfactorily be overcome by using purely isolated environmentally relevant chlorinated bornane derivatives (Parlar Nr. 26, 32, 50, 42, 69). The method is highly selective for measuring Toxaphene residues in complex marine organism matrices.

Concentrations of toxaphene (polychlorinated monoterpenes, chlorobornanes) were determined in human milk samples from Nicaragua and in fish from the North Sea. Relatively high toxaphene levels were found in the Nicaraguan human milk samples. The lack of correlation between the number of children of the mothers and toxaphene levels in their milk suggests a compensation of the elimination of toxaphene by a regularly high toxaphene intake. The increasing trend of toxaphene concentrations in North Sea fish sampled further away from the European coast suggests an aerial transport of toxaphene from the American continent to Europe.

In order to interpret present and predict future environmental concentrations of persistent organochlorine pesticides in remote regions information on historical and future trends in emissions and use of these compounds on a global scale is required. Through contact with international agencies, literature surveys and other means information on registration status, trends in regional use/emissions, mode and time of application as well as representative soil concentrations of ten pesticides are been compiled. Data of global toxaphene usage were collected for more than 50 countries around world. The accounted for cumulative global toxaphene usage were estimated to be 450,000 tonnes, the interpolated usage from 1950 to 1993 were 1,330,000 tonnes and from 1970 to 1993 were 670,000 tonnes. Toxaphene is still being in applied eg. in former Soviet Union and in Mexico. International cooperation and improved record keeping by governments are required to improve the estimates.

Pooled samples of homogenized Guillemot eggs from 1974, 1978, 1982 and 1987 and ten individual eggs for each of the two years, 1976 and 1989 have been analyzed for PCC with GC-ECD and GC-MS in the ECNI mode. Regression analysis on PCC concentrations versus sampling year, using the results obtained in GC-ECD analyses based on pooled egg samples and the mean values of the egg samples from 1976 and 1989 respectively, revealed a significant (p

In the past five years the National Institute of Standards and Technology (NIST) has developed several Standard Reference Materials (SRMs) to assist in the validation of measurements of polychlorinated biphenyl (PCB) congeners and chlorinated pesticides in environmental samples. The following natural matrix SRMs have been issued: SRM 1588, Organics in Cod Liver Oil; SRM 1939, PCB Congeners in River Sediment; SRM 1941, Organics in Marine Sediment; SRM 1974, Organics in Mussel Tissue (Mytilus edulis); and SRM 1945, Whale Blubber. All of these SRMs have been analyzed for selected PCB congeners and chlorinated pesticides, and three of these materials (SRMs 1939, 1941, and 1974) have also been analyzed for polycyclic aromatic hydrocarbons (PAHs). In 1982, SRM 1649, Urban Dust/Organics, was issued with certified concentrations for selected PAHs. Recently, SRM 1649 has been analyzed for selected PCB congeners and chlorinated pesticides. Toxaphene measurements have not been made at NIST for these SRMs; however, these SRMs represent the environmental matrices that are typically analyzed for toxaphene. Recommended values for toxaphene concentrations could be established on any of these materials through interlaboratory comparison exercises involving laboratories experienced in making toxaphene measurements. In this paper we describe these SRMs and discuss their suitability as potential reference materials for toxaphene measurements.

An electron capture negative ion mass spectrometric method for quantitative determination of chlorobornanes was tested on selected samples from an arctic marine food chain. The method provided sufficient sensitivity to detect residues down to 0.3 ppb. Detailed area counts at prescribed mass scans were collected and processed for two selected samples, a fish and a neuston sample. Total chlorobornane concentrations were, 1.6 ng/g for the neuston and 12.8 ng/g for the pollack. Chlorine homologue class (Cl 6 to Cl 10 ) concentrations for each sample were determined. Relative homologue amounts linked the neuston to an atmospheric input since it had highest concentrations of Cl 6 , which is more prevalent in air, while the fish had a higher relative levels of Cl 8 and Cl 9&10 homologues indicative of the tendency for these more lipophilic homologues to concentrate in fish lipids.

The gaschromatographic determination of Toxaphene and its residues in different environmental compartments is often difficult. This problem can satisfactorily be overcome if purely high chlorinated bornane derivatives are available. In the present work it was able to isolate large quantities of eleven of these highly chlorinated Toxaphene components (7–17) and to elucidate their structures with the help of spectroscopical methods.

The theoretical number of chlorinated bornanes, the basic skeleton of toxaphene, has been determined. In addition, the distribution on different chlorine content as well as a short consideration of the symmetry and optical isomerism is given.

The HRGC-determination of Taxophene® residues in the presence of other chlorinated hydrocarbons with similar retention times is often difficult. This problem can satisfactorily be overcome by using purely isolated high-chlorinated bornane derivatives (7–17) as standard. The method is highly selective for measuring toxaphene in complex environmental matrices, such as fish, and can also be used for evaluating the changes in the relative distribution that may have resulted from bioaccumulation and environmental transformation.

Toxaphene was a heavily used, broad-spectrum insecticide, which was banned in most countries in the 1980s. Early data suggested that a limited number of congeners in the technical mixture were responsible for its toxicity to insects. However, toxaphene research has historically focused on analyzing total toxaphene, largely due to insufficient analytical methodology to measure the individual congeners. In recent years, congener-specific toxaphene research has flourished due to analytical advances leading to the identification of several congeners, about 25 of which are commercially available. However, the high price of these standards may inhibit toxaphene research in some laboratories. We report here the methylene retention indexes for 28 isolated toxaphene congeners. When used in conjunction with mass spectrometry, methylene retention indexes provide an alternative method for identifying these compounds when direct comparison with standard compounds is not practical.

In 2003 is ten behoeve van het ministerie van Landbouw, Natuur en Voedselkwaliteit (LNV) programma 378, “Bewaking van de kwaliteit en veiligheid van land-, tuinbouw- en visserijproducten” (momenteel programma 438, gecoördineerd door het RIKILT Instituut voor Voedselveiligheid), opgestart waarbij als onderdeel van dit programma jaarlijks gehalten van organische microverontreinigingen in kabeljauw- en heeklever worden gemeten. Dit deelonderzoek is uitgevoerd naar polychloorbifenylen (PCBs), organochloor pesticiden (OCPs) en toxafeen.

In 2003 is ten behoeve van het ministerie van Landbouw, Natuur en Voedselkwaliteit (LNV) programma 378, “Bewaking van de kwaliteit en veiligheid van land-, tuinbouw- en visserijproducten” (momenteel programma 438, gecoördineerd door het RIKILT Instituut voor Voedselveiligheid), opgestart waarbij als onderdeel van dit programma jaarlijks gehalten van organische microverontreinigingen in kabeljauw- en heeklever worden gemeten. Dit deelonderzoek is uitgevoerd naar polychloorbifenylen (PCBs), organochloor pesticiden (OCPs) en toxafeen.

(2000). Are Chlorinated Pesticides a Causation in Maternal Mitochondrial DNA (mtDNA) Mutations? Archives of Environmental Health: An International Journal: Vol. 55, No. 5, pp. 292-294.

HPGC-ECD- und HPGC-NCI-SIM-Untersuchungen an kommerziell erhaltlichen Toxaphenstandards bezuglich deren Detektions-Eigenschaften beweisen, das ihre relativen Empfindlichkeiten sehr stark vom jeweiligen Chlorgehalt des Standards beeinflust werden. Dies bedeutet, das man bei der Quantifizierung von Umweltproben nur dann genaue Werte erhalten kann, wenn die untersuchten Proben und der benutzte Standard gleiche oder zumindest ahnliche Detektoreigenschaften aufweisen. Wenn keine vergleichbaren Standards zur Verfugung stehen, dann kann auch ein beliebiger Standard benutzt werden, sofern man anschliesend die Ergebnisse mit einem Korrekturfaktor verrechnet. Vergleicht man verschiedene Integrationsmethoden, dann zeigt sich, das man die sichersten Ergebnisse durch Integration moglichst vieler Einzelsignale erhalt. Eine Quantifizierung durch Auswertung der gesamten Flache oder des Buckels, der durch den Anstieg der Basislinie entsteht, ist dagegen nicht zu empfehlen, weil dieser Bukkel durch temperaturabhangige Zersetzungsprozesse verursacht wird, deren Ausmas vom Chlorgehalt des Toxaphens beeinflust wird. Da der Cl-Gehalt in Umweltproben aufgrund von Umwandlungen und Akkumulationsprozessen anders ist als der der Standards, fuhrt die Integration der Buckelflache zu fehlerhaften Ergebnissen.

Quantitation of camphechlor/toxaphene in biological matrices like cod-liver oil or fish is difficult because it is a very complex mixture of alicyclic polychlorinated compounds. Furthermore, many toxaphene components are biotransformed and photodegraded and the complex mass spectral fragmentation pattern of HRGC/MSD (electron impact (EI)) cannot be used for quantitation at the μg/g-level or below. The use of several indicator-peaks after ECD-detection using the technical standard mixture for calibration does not characterize the entire pattern in a biological sample. Two averaging integration methods that are based on the entire HRGC/ECD-pattern of toxaphene compounds after separation from the PCB congeneres by adsorption chromatography on silicagel, allow a fast and accurate quantitation of the mixture in biological samples, e.g. cod-liver oil. Biological degradation does not disturb the determination because the whole pattern of the complex mixture is considered instead of only a few compounds of the parent mixture which could be degraded or not.