Environ. Sci. Technol. 1999, 33, 2346-2351

In 1972, DDT was banned in the United States except for DDT Metabolite emergency control of vector-borne diseases. Most other industrialized countries, including West , also Bis(Chlorophenyl)acetic Acid: The banned the use of DDT in the early 1970s. In the former Neglected Environmental German Democratic Republic (GDR), however, DDT was still produced and used until the end of the 1980s, and some Contaminant developing countries still use DDT (4-7), especially for vector- borne disease control (8). Voldner and Li (4) estimated the THOMAS HEBERER* cumulative global usage of DDT between 1950 and 1993 at Institute of Food Chemistry, Technical University of , 2.6 million t with 990 000 t from 1970 to 1993. Gustav-Meyer-Allee 25, D-13355 Berlin, Germany DDT residues are distributed globally by atmospheric transport (9). They are also found in arctic mammals (10). ¨ UWE DUNNBIER Further studies began to unravel the endocrinal effects of Berlin Water Works, Department of Laboratories, DDT residues in wildlife. The studies suggest that some P.O. Box 310180, D-10631 Berlin, Germany isomers of DDT derivatives act as endocrine-disrupting chemicals causing emasculation, abnormal sexual develop- ment, and impaired reproduction in wildlife (11-15). Ad- ditionally, studies by Kelce et al. (16) have shown that p,p′- Up to the present date, DDA (2,2-bis(chlorophenyl)acetic DDE is a potent androgen receptor antagonist. Pereira et al. acid) resulting from the degradation of DDT (2,2-bis- (17) concluded that the environmental effects of DDT and (chlorophenyl)-1,1,1-trichloroethane) residues in the its derivatives would begin to manifest themselves several environment has been neglected as an environmental decades after the introduction of these compounds. contaminant of the aquatic system. More than 60 years DDT residues are extremely persistent in the environment after the invention of DDT as an insecticide and more than and degradation strongly depends on the environmental 25 years after its use was banned in most of the developed conditions. In investigations of DDT in the Lauritzen Canal countries, DDA was found as major contaminant up to and in Richmond Harbor in San Francisco Bay, Pereira et al. the microgram per liter level in the surface water of the (17) found that under anaerobic conditions DDT is reductively Teltowkanal in Berlin, Germany. DDA is formed together with dechlorinated primarily to DDD, whereas under aerobic some other intermediates of DDT such as DDD (2,2-bis- conditions it is mainly dehydrochlorinated to DDE and to a (chlorophenyl)-1,1-dichloroethane), DDE (2,2-bis(chlorophe- lesser degree to dichlorobenzophenone (DBP). However, in nyl)-1,1-dichloroethylene), DDMU (2,2-bis(chlorophenyl)-1- zones with high DDT residue concentrations, aerobic deg- radation was found to be diminished or inhibited (17). Pereira chloroethylene), DDOH (2,2-bis(chlorophenyl)ethanol), et al. (17) also described environmental findings of DDMU DDMS (2,2-bis(chlorophenyl)-1-chloroethane), DDCN (2,2- (2,2-bis(chlorophenyl)-1-chloroethylene), another important bis(chlorophenyl)acetonitrile), and DBP (dichloroben- degradation product of DDT, and its derivatives. In 1998, zophenone), which were identified at lower concentrations Quensen et al. (18) in laboratory experiments also found in surface water of the canal. Our results add some new DDMU as an important degradation product mainly deriving aspects to the ongoing controversy over the fate of DDT in from DDE residues that were for a long time regarded as the natural environment and confirm some laboratory terminal residues in the environment. These findings started experiments about the natural remediation of DDT residues. a new controversy over whether persistent DDT residues Moreover, the polar degradation product DDA is also a can be naturally degraded by microbial action and whether potential problem for drinking water production because it the laboratory results can be transferred to the natural is the only DDT derivative that also leaches into the conditions found at DDT-contaminated Superfund sites (19). groundwater wells of a neighboring drinking water plant Despite all these discussions, it is difficult to believe that at concentrations exceeding the European maximum tolerance until now DDA, the polar metabolite of DDT, DDD, DDE, levels for pesticide residues in drinking water. and DDMU, has not been recognized in any of the many investigations of DDT residues in the aquatic environment. Many positive findings of DDT residues in seawater, surface Introduction water, groundwater, or drinking water have been reported At the end of the 1930s, Paul Mu¨ller discovered the insecticidal worldwide; some of these being recent publications (20- properties of 2,2-bis(chlorophenyl)-1,1,1-trichloroethane 29). However, DDA has never been included in these (DDT) (1). In the following decades, DDT was used worldwide investigations, although DDA was one of the first DDT as highly active insecticide in agriculture, for pest control in metabolites to be known. In 1945, it was isolated and forestry and for vector control in human hygiene against identified by White and Sweeney (30) in the urine of rabbits diseases such as malaria and typhus. In the 1960s, there was exposed to DDT. Ware et al. (31) called DDA “perhaps the some evidence that DDT and its metabolites DDE (2,2-bis- universal DDT metabolite in microorganisms, plants, insects, (chlorophenyl)-1,1-dichloroethylene) and DDD (2,2-bis- and higher animals”. DDT is also converted readily into DDA (chlorophenyl)-1,1-dichloroethane) are highly persistent in by purely chemical action or by photodecomposition (31). the environment and accumulate in higher animals (2, 3). In 1978, Marei et al. (32) detected DDA as one important Other studies have shown that DDT derivatives are toxic and metabolite on incubation of DDT with sewage sludge in responsible for the thinning of egg shells of birds (3). laboratory experiments. They also postulated the occurrence * Corresponding author telephone: ++49 30 314-72796; fax: ++49 of DDA in the aquatic environment; nevertheless, we could 30 314-72823; e-mail: [email protected]; inter- not find any reliable data in the literature about the net: http://stanpc1.lb.tu-berlin.de/lc/heberer.htm. occurrence of DDA.

2346 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 33, NO. 14, 1999 10.1021/es9812711 CCC: $18.00  1999 American Chemical Society Published on Web 05/29/1999 FIGURE 1. Map showing the 10 sampling locations in the river Dahme and Teltowkanal in July 1997. All samples were taken in the middle of the water courses at a depth of 2 m.

In 1996, in investigations of drug residues that were found to a procedure described elsewhere (39). Solid-phase extrac- in the groundwater wells of a Berlin drinking water plant tion (SPE) was carried out with a vacuum manifold (spe 12G) (33), we also identified residues of DDA at concentrations using cartridges of polypropylene with a volume of 6 mL and reaching the microgram per liter level (34). Further inves- end-capped RP-C18 or Bakerbond Polar Plus RP-C18 material tigations of the neighboring water course concerning DDT all from Mallinckrodt Baker (Griesheim, Germany). residues were carried out to identify the contamination Sample Collection. As shown in Figure 1, 10 representative sources and to evaluate the importance of DDA in the aquatic sampling locations were selected for the screening of the system. The results of these investigations presented here surface water at the DDT contaminated Superfund site in show that DDA is not just one derivative but is the major the Teltowkanal in Berlin, Germany. The samples were DDT derivative in the aqueous phase of the Teltowkanal in collected with standard equipment from the middle of the Berlin. Furthermore, the results confirm many of the waters at a depth of 2 m. All samples were stored at 4 °C until postulations made by Marei et al. (32) and add some new they were extracted and analyzed for DDT residues on the aspects to the debate concerning the fate of DDT residues next day. in the environment. Sample Preparation for Nonpolar DDT Derivatives. A Experimental Section water sample of 0.5 L was adjusted to a pH of 8.5 for SPE. Each SPE cartridge was filled with1gofanend-capped RP- Analytical Methods. DDA was analyzed according to an C18 adsorbent. Conditioning was performed successively analytical method originally developed for the analysis of - with 10 mL of acetone, 10 mL of methanol, and finally 10 mL polar pesticides and drug residues (35 38). This method of distilled, deionized water. The solvents were drawn through applies solid-phase extraction (SPE) using a non-end-capped the cartridges by means of a gentle vacuum, and the cartridge reversed-phase octadecyl material (RP-C18), derivatization was not permitted to run dry during the whole conditioning with pentafluorobenzyl bromide (PFBBr), and analysis with - - procedure. The water sample was then percolated through capillary gas chromatography mass spectrometry (GC MS) the cartridge at a maximum flow rate of approximately 8 in selected ion monitoring (SIM) mode. The nonpolar DDT mL/min by applying a low vacuum. derivatives were extracted by SPE using an end-capped RP- - C18 material (38). The elutes from SPE were analyzed applying After the cartridge was dried for 2 3 h by flushing with GC with electron capture detection (ECD) and for confirma- nitrogen, the analytes were eluted from the cartridge with tion purposes GC-MS with SIM (38). Additionally, for the dichloromethane and toluene. The eluate was dried under confirmation of the identity of the DDT derivatives, samples a gentle stream of nitrogen. The residue from the sample were analyzed by tandem mass spectrometry (GC-MS/MS). preparation was dissolved in 100 µL of toluene and injected Materials. All solvents were highly purified products from directly into the gas chromatograph. Merck (Darmstadt, Germany). Pentafluorobenzyl bromide Sample Preparation for o,p′- and p,p′-DDA. A water was obtained from Aldrich (Steinheim, Germany); triethy- sample of 0.5 L was mixed with 100 µL of a solution of 2-(4- lamine was from Merck (Darmstadt, Germany). Sample vials, chlorophenoxy)butyric acid in methanol (1 mg/L) as sur- screw caps, and septa were purchased from Zinsser (Frank- rogate standard to give a concentration of 200 ng/L. The furt, Germany); 200-µL inserts for the sample vials from CS- sample was adjusted to a pH <2 before SPE. Each SPE Chromatographie Service (Langerwehe, Germany). DDT, cartridge was filled with1gofanon-end-capped RP-C18 DDD, DDE, DDMU, DDOH, DDA, DBP, and the internal adsorbent. Conditioning was performed successively with standard 2-(2-chlorophenoxy)propionic acid were of analyti- 10 mL of acetone, 10 mL of methanol, and finally 10 mL of cal purity and purchased from Promochem (Wesel, Ger- distilled, deionized water (pH < 2). The solvents were drawn many), from Riedel de Haen (Seelze, Germany), or from through the cartridges by means of a gentle vacuum, and the Aldrich (Deisenhofen, Germany). The surrogate standard cartridge was not permitted to run dry during the whole 2-(4-chlorophenoxy)butyric acid was synthesized according conditioning procedure. The water sample was then per-

VOL. 33, NO. 14, 1999 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 2347 TABLE 1. Results from the Surface Water Monitoring of DDT Residues in the Teltowkanal in Berlin, Germanya sampling surface o,p′-DDT p,p′-DDT o,p′-DDE p,p′-DDE o,p′-DDD p,p′-DDD o,p′-DDAb p,p′-DDA location no. water (ng/L) (ng/L) (ng/L) (ng/L) (ng/L) (ng/L) (ng/L) (ng/L) 1 Dahme ndc nd nd nd nd <5ndnd 2 Dahme nd nd nd nd nd nd nd nd 3 Dahme nd nd <5ndnd <5ndnd 4 Teltowkanal nd nd nd nd <5 <5ndnd 5 Teltowkanal nd nd nd <5 35 80 110 330 6 Teltowkanal nd nd nd 5 50 140 210 760 7 Teltowkanal nd nd nd <5 10 40 55 180 8 Teltowkanal nd nd nd nd 10 15 40 165 9 Teltowkanal nd nd nd <1 <5103080 10 Teltowkanal nd nd nd nd nd 10 35 125 a The results represent the average of a 3-fold determination of each sample. b o,p′-DDA was not commercially available; therefore, the p,p′-DDA standard was used for its quantitation. 500 mL of the water samples has been processed in sample preparation. The recoveries for all compounds were better than 70%. The limits of detection were below 1 ng/L for all compounds. The limits of quantitation were always below 5 ng/L. c nd, not detected. colated through the cartridge at a maximum flow rate of in corresponding time windows. The tuning of both mass approximately 8 mL/min by applying a low vacuum. spectrometers was performed weekly using the autotuning After the cartridge was dried for 2-3 h by flushing with macro. Precolumns and/or insert liners were exchanged after nitrogen, o,p′- and p,p′-DDA were eluted with methanol. An 50 injections at the latest. internal standard (2-(2-chlorophenoxy)propionic acid) was added, and the eluate was dried under a gentle stream of Results and Discussion nitrogen. The residue was then derivatized to make o,p′- and DDT Contaminated Superfund Site in the Teltowkanal in p,p′-DDA amenable to gas chromatography. Berlin. The Teltowkanal in the south of Berlin was built Derivatization of DDA. Derivatization was performed at between 1901 and 1906. The canal was used as drainage for 110 °C for 1 h using 100 µL of PFBBr (2% in toluene) and 2 rainwater and industrial wastewater from districts formerly µL of triethylamine as the catalyst as described elsewhere located outside of Berlin. Additionally, it was used as a (40). The derivatized sample was then dried under nitrogen, shipping canal for industrial supply and as a short cut for the dissolved in 100 µL of toluene, and injected into the gas shipping routes between the rivers and . The canal chromatograph. has a length of approximately 35 km and connects the rivers Analysis Applying GC-ECD. All GC-ECD measurements Dahme and . At the beginning of the Teltowkanal close were performed with an HP-5890A gas chromatograph from to the confluence of the river Dahme with the canal, a large Hewlett-Packard (Waldbronn, Germany) equipped with an chemical production plant is located (Figure 1). In this autosampler HP-7673A and fitted with a 50 m × 0.32 mm production plant in former East Berlin more than 60 000 t fused-silica capillary column HP-5 with 0.17 m film thick- µ of DDT were produced and formulated between 1943 and ness. Carrier gas was helium (purity, 99.999%). The oven 1986 (41). It is an open secret that production residues were temperature was held at 100 °C for 1 min following injection, released into the soil and into the neighboring water course, then programmed at 30 °C/min to 150 °C, which was held the Teltowkanal. It is, however, not clear when and how much for 1 min, then at 3 °C/min to 205 °C followed by 10 °C/min DDT was discharged into the canal. to 260 °C, and finally held for 23 min. Injection of 1 µLofthe sample was performed hot splitless at 210 °C with the split DDT Residues in the Teltowkanal Sediment. Random closed for 0.9 min. The detector temperature was set to 300 canal sediment samples were collected and analyzed for DDT °C. residues (34). Total DDT concentrations up to more than 1 - - mg/kg (dry weight) were found in these samples. Interestingly, Analysis by GC MS and GC MS/MS. Mass spectrometric ′ ′ measurements were performed using an Hewlett-Packard DDT (o,p - and p,p -DDT) itself was only detected at HP 5970 MSD combined with an HP 5890 gas chromatograph maximum concentrations of 0.05 mg/kg. It has almost totally fitted with a 25 m × 0.2 mm i.d. × 0.33 µm HP-5 capillary been converted to DDD, which was found at concentrations column and a 1.5 m × 0.32 mm i.d. × 0.33 µm HP-5 up to more than 1 mg/kg. DDE was produced to a lesser precolumn. Additionally, mass spectrometric measurements extent and detected at maximum concentrations of 0.2 mg/ were performed with a Finnigan GCQ iontrap GC-MS/MS kg in the sediment samples. DDA was not detected at system fitted with a 30 m × 0.25 mm i.d. × 0.25 µm J&W significant concentrations in the sediment. The DDD residues DB5MS capillary column. In both cases, carrier gas was dominating in the sediments of the canal clearly indicate helium (purity, 99.999%) set to a flow of 28 cm/s at the initial that DDT was converted under almost anaerobic conditions, temperature. The oven temperature was held at 100 °C for as shown by Pereira et al. (17) in San Francisco Bay. 1 min following injection, then programmed at 30 °C/min Occurrence of DDA and Other DDT Derivatives in the to 150 °C, which was held for 1 min, then at 3 °C/min to 205 Surface Water. Surface water samples were collected in July °C followed by 10 °C/min to 260 °C, and finally held for 23 1997 from the river Dahme and the Teltowkanal up to the min. Injection port and transfer line temperatures were 230 bank filtration area of a drinking water plant close to the and 250 °C (GCQ, 275 °C), respectively. The 2-µL quantities canal (Figure 1). The purpose of these investigations was to of sample were injected using hot splitless injection with the identify DDT residues, to investigate their distribution in the split closed for 0.9 min. Using selected ion monitoring (SIM), canal, and to determine the individual ratios of the DDT three characteristic ions were selected for each compound derivatives present in the aqueous phase. Some results of and scanned in time windows corresponding to their these investigations are compiled in Table 1. expected retention times with dwell times of 150-300 ms/ DDA was found at maximum concentrations up to 1000 ion. Using the GCQ in the MS-MS mode, suitable parent ng/L and is clearly the dominant DDT derivative in the ions were selected for each analyte, which were fragmented aqueous phase of the canal. The individual ratios of the o,p′- again. The resulting daughter ion mass spectra were scanned and p,p′-isomers reflect the ratios of o,p′- and p,p′-DDT in

2348 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 33, NO. 14, 1999 FIGURE 2. MID chromatogram recorded with GC-MS applying SIM of the derivatized extract of a surface water sample collected from the Teltowkanal (no. 5) in Berlin, Germany. This sample contained 110 ng/L of o,p′-DDA and 330 ng/L of p,p′-DDA. Extracted sample volume: 500 mL; 102% recovery was measured for the surrogate standard (2-(4-chlorophenoxy)butyric acid) added at a concentration of 200 ng/L. ISTD: 2-(m-chlorophenoxy)propionic acid.

FIGURE 3. Indicative ion traces (m/z 235, 237, and 460) for the PFB esters of o,p′- and p,p′-DDA extracted from the MID chromatogram shown in Figure 2. FIGURE 4. Proposed degradation pathway of DDT residues in the Teltowkanal. Names of DDT derivatives are printed in bold when the technical product. This indicates that there is no they were found in our investigations. Names of derivatives that significant stereoselectivity in the environmental metabolism were found as key metabolites in the aqueous phase are underlined. of DDT to DDA. DDD, which is the second important DDT derivative in the surface water of the canal, was detected at DDD, which dissolves even better in the aqueous phase than concentrations on average five times lower than those of DDT or DDE. DDD is converted to DDA, which seems to be DDA. Additionally, some other DDT derivatives such as o,p′- a very persistent key metabolite in the aquatic system. Figure and p,p′-DDMS (2,2-bis(chlorophenyl)-1-chloroethane), o,p′- 4 shows a possible degradation pathway of DDT to DDA in and p,p′-DDCN (2,2-bis(chlorophenyl)acetonitrile), p,p′-DBP, the Teltowkanal. This pathway is derived mainly from the and p,p′-DDOH (2,2-bis(p-chlorophenyl)ethanol) were also known anaerobic reductive metabolism of DDT observed in found in these samples at lower concentrations. DDT was microorganisms in laboratory experiments (42, 43). The DDT however not detected in any of the water samples, and DDE metabolites that have been detected at considerable con- and p,p′-DDMU were only found at trace levels in a few centrations in the surface water of the Teltowkanal are samples. All analytes were identified by their retention times underlined. p,p′-DDMU, which is only found at trace-level and/or mass spectra using GC-MS and GC-MS/MS. DDCN concentrations, may be formed from DDD or mainly from was identified by its electron ionization mass spectrum, which DDE as proposed by Quensen et al. (18). The very low was published by Albone et al. (44). concentrations of p,p′-DDMU and DDE as compared to those Figure 2 shows a typical multiple ion detection (MID) of DDD, DDA, or DDMS may support this proposal. o,p′- chromatogram recorded with GC-MS applying SIM acquisi- and p,p′-DDMS are intermediate metabolites in the degra- tion of a derivatized extract of a surface water sample collected dation of DDD to DDA. DDD may also be dechlorinated from the Teltowkanal (no. 5). As shown in Figure 3, the PFB directly to DDMS without the intermediate formation of esters of o,p′- and p,p′-DDA have been unequivocally DDMU (42, 43). identified and quantified by their indicative ion traces at DBP may be formed together with DDE under aerobic m/z 235, 237 (characteristic chlorine cluster ions), and 460 conditions as reported by Pereira et al. (17). DBP is however (molecular ion of o,p′- and p,p′-DDA PFB ester). Applying also described as a photodegradation product of DDA (31). GC-MS with SIM, both analytes could be detected and Remarkably, only the p,p′-isomer but no o,p′-DBP was quantified in environmental water samples down to the low detected in the surface water, which should occur when DPB nanogram per liter level independent of the amount and is built from DDA by photodegradation. composition of the environmental matrix. The quantitation DDCN, which is also found in the Teltowkanal, was of the analytes was performed using external calibration. reported by Albone et al. (44) to be formed under anaerobic The surrogate standard was added before analysis and used conditions in sewage sludges. It was also found by Jensen et to control the whole analytical procedure including recovery al. (45) in investigations of lake sediments. It is however not control (36). The internal standard is used to control the clear whether DDCN is formed directly from DDT or from derivatization step and the GC injection (36). In all analyses DDA (44). for DDA residues, the recovery of the surrogate was between The occurrence of the DDT residues only at sampling 82 and 107%. location nos. 5-10 clearly identified the chemical production The results of our investigations indicate that in the plant as the contamination source. Downstream of the canal Teltowkanal DDT is metabolized mainly anaerobically to at sampling location no. 6, the maximum concentrations

VOL. 33, NO. 14, 1999 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 2349 for all DDT derivatives were measured. In 1989, water samples persistent in the environment, and as shown here, it leaches from this sampling site were analyzed for DDT residues (DDT, easily through the subsoil into the groundwater aquifers. DDD, DDE, and DDMU) by Heinisch and Wenzel (46). DDA has thus become a problem in the Teltowkanal area Heinisch and Wenzel found p,p′-DDD as the major con- where groundwater recharge is used in drinking water taminant at concentrations of 140 ng/L. This value corre- production. DDT residues have finally been converted to a sponds exactly to our result for p,p′-DDD at the same location less toxic form, but they obviously do not disappear 8 years later. Thus, there is some indication that there has completely by mineralization. In our example of the Tel- been little or no change in the degree of DDT contamination towkanal, the problem of the DDT residues has been shifted of the aqueous phase during all these years. It seems as if by the natural degradation of DDT from the sediments to the there is a steady-state condition in the Teltowkanal where surface water and finally into the groundwater aquifers, the aqueous phase is continuously fed by DDT residues making DDT residues problematic for drinking water pro- accumulated in the canal sediment. Heinisch and Wenzel duction when regarding the maximum tolerances for pes- (46) should also have found DDA in their investigations, but ticides in drinking water set by the EU (47). This problem it was unfortunately not included in the analytical program. will remain in the future because of DDA’s persistence in the DDA Residues in the Groundwater Wells of a Drinking contaminated groundwater aquifers. Water Plant. As shown in Figure 1, a drinking water plant If the situation of the Teltowkanal is comparable to other that uses up to 62% of bank filtrate in drinking water DDT-contaminated Superfund sites, DDA should also be production is located downstream of the canal. Using bank found there. In our investigations DDA accounts for more filtration, the surface water from the Teltowkanal is expected than 60% of the total DDT residues found in the aqueous to be clarified of microorganisms and micropollutants. phase of the Teltowkanal. The concentrations of DDA were Nevertheless, polar organic contaminants such as drug on average five times higher than those measured for DDD. residues (33) and DDA are found in groundwater wells from DDD is analyzed as one standard parameter in water analysis. the bank filtration area. We detected o,p′- and p,p′-DDA at It seems probable that DDA might have been present at individual concentrations up to 0.28 and 1.7 µg/L, respectively considerable concentrations in those samples that have been (34). The DDA concentrations are even higher than those reported to contain residues of DDD. In conclusion, DDA measured in the Teltowkanal directly in front of the bank can be seen as an important parameter that should be filtration area. This might be explained by higher DDA intakes analyzed whenever surface water, groundwater, and drinking in the past and indicates the persistence of DDA residues in water samples are investigated concerning DDT residues. the groundwater aquifers. It can also be concluded that polar contaminants leach easily through the subsoil into the Acknowledgments groundwater aquifers because polar drug residues are also The authors thank Kathrin Schmidt-Ba¨umler and Gudrun found at concentrations comparable to those detected in Fricke for their practical assistance and Bob Hatton and Hans- the canal (35). In Berlin, polar contaminants are also a Ju¨rgen Stan for reviews. problem in drinking water production because there is no special purification of the resulting raw waters, e.g., activated Literature Cited carbon is not used. Thus, the Berlin water works closed down (1) Ro¨chling, H. In Chemistry of plant protection and vector control several of the drinking water wells to keep the DDA agents. Vol. 1; Wegler, R., Ed.; Springer-Verlag: Berlin, 1970; pp concentrations below the maximum tolerance levels for 121-128. pesticide residues in drinking water set to 0.1 µg/L by the (2) World Health Organization. Environmental Health Criteria (EHC) - European Union (47). 83: DDT and its derivatives Environmental Aspects; WHO: Geneva, 1989. The public authorities have recently initiated a first (3) Korte, F., Ed.; Textbook of ecological chemistry. Basics and monitoring program to investigate the degree of groundwater concepts for the ecological assessment of chemicals ; Thieme- contamination by DDA residues in this area. The results of Verlag: Stuttgart, 1992. these investigations should enable the assessment of ground- (4) Voldner, E. C.; Li, Y. F. Sci. Total Environ. 1995, 160/161, 201- water contaminations caused by DDT residues that have 210. (5) Mitra, J.; Raghu, K. Bull. Environ. Contam. Toxicol. 1998, 60, been released into the Teltowkanal and into the soil of the 585-591. chemical production plant. (6) Phoung, P. K.; Son, C. P. N.; Sauvain, J.-J.; Taradellas, J. Bull. Why Has DDA Been Neglected as an Environmental Environ. Contam. Toxicol. 1998, 60, 347-354. Contaminant until Now? Although, it is hard to believe, it (7) Pardio, V. T.; et al. Bull. Environ. Contam. Toxicol. 1998, 60, - is easy to see why DDA has not been analyzed for in all 852 857. (8) Hayes, W. J., Jr. Handbook of Pesticide Toxicology, Vol. 2; systematic investigations of DDT residues in the aquatic Academic Press: New York, 1991; pp 743-774. environment. DDT derivatives such as DDT, DDD, DDE, (9) Larsson, P.; et al. Naturwissenschaften 1995, 82, 559-561. DDMU, and DBP can be analyzed together in multiresidue (10) Letcher, R. J.; Norstrom, R. J.; Muir, D. C. G. Environ. Sci. Technol. methods developed for the analysis of nonpolar contami- 1998 , 32, 1656-1661. nants. However, due to its polar structure, DDA has to be (11) Colborn, T.; vom Saal, F. S.; Soto, A. M. Environ. Health Persepect. - analyzed for separately. In the analysis of DDA residues in 1993, 101, 378 384. (12) Guillette, L. J., Jr.; et al. Environ. Health Perspect. 1994, 102, water samples there are several steps in the analytical 680-688. procedure that are totally different from those used for the (13) Sharpe, R. M. Nature 1995, 375, 538-539. analysis for the other DDT derivatives, e.g., the water samples (14) Toppari, J.; et al. Environ. Health Persepect. 1996, 104, 741-803. need to be acidified before extraction, DDA has to be (15) Schlumpf, M.; Lichtensteiger, W. Z. Umweltchem. O¨ kotox. 1996, derivatized to render it amenable to gas chromatographic 8, 321-332. - analysis, and the use of mass spectrometry instead of electron (16) Kelce, W. R.; et al. Nature 1995, 375, 581 585. (17) Pereira, W. E.; Hostettler, F. D.; Rapp, J. B. Mar. Environ. Res. capture detection (ECD) is a prerequisite for the analysis of 1996, 41, 299-314. DDA. If one of these prerequisites is lacking, DDA will not (18) Quensen, J. F., III; Mueller, S. A.; Jain, M. K.; Tiedje, J. M. Science even be found by chance. 1998, 280, 722-724. 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