Determination of Polar Organic Pollutants in Aqueous Samples of Former Ammunition Sites in Lower Saxony by Means of HPLC/Photodiode Array Detection (HPLC/PDA) and Proton Nuclear Magnetic Resonance Spectroscopy ( 1H-NMR)

Leachate, ground-, and surface water from former ammunition sites and areas which are known to be contaminated by nitroaromatic compounds in Lower Saxony (Germany) were investigated in order to identify and quantify acidic nitroaromatic compounds (e.g., nitrobenzoic acids, aminonitrobenzoic acids, nitrophenols, and nitrocresols). Acidic and neutral nitroaromatic compounds were enriched by solid-phase extraction (SPE) on a polystyrenedivinylbenzene copolymer and routinely screened for acidic compounds by means of HPLC/photodiode array detection (HPLC/PDA). Qualitative and quantitative results obtained in this way were corroborated by proton nuclear magnetic resonance spectroscopy (¹H-NMR). Validation data for the quantification procedure using this technique are given. The results show that all samples contaminated with 2,4,6-trinitrotoluene (TNT) and related compounds are also contaminated by acidic nitroaromatic compounds (e.g., 2,4-dinitrobenzoic acid, 3,5-dinitrophenol, and especially with 2-amino-4,6-dinitrobenzoic acid) in the μg/L range. This current work shows that 1 H-NMR allows the quantitative determination of protoncarrying analytes in mixtures after solid-phase extraction down to the upper ng/L range after addition of an internal standard to the SPE extract. This is even possible when reference compounds are not commercially available.     

Organochlorine compounds in bottom sediments,benthos, and fish in the volga pool of the Rybinsk Reservoir

The concentrations of three groups of organochlorine compounds (HCCH, DDT, and PCB) in bottom sediments, zebra mussel, and two fish species—zope and roach—in the Volga Pool of the Rybinsk Reservoir. The concentrations of the examined toxicants can be ranked in the ascending order as follows: HCCH<DDT<PCB. The total concentration of organochlorine compounds (OCC) and their metabolites are very low, thus allowing the Volga Pool to be regarded as a background region for the Upper and Middle Volga Basin. A congener-specific determination of PCB was carried out, and priority congeners were identified for monitoring the ecosystem pollution by dioxin-like compounds.     

Concentrations of PCBs in coastal mangrove sediments of Hong Kong

The concentrations of polychlorinated biphenyls (PCBs) in surface sediments of ten mangrove sites in Hong Kong were determined by Congener-specific and Arcolor methods. Spatial variations were found between mangrove sites and within the same site, indicating that the sediment samples were heterogeneous and total PCBs concentrations in mangrove sediments should be normalised to compensate for natural variability and for identifying serious anthropogenic contamination. In addition to total organic carbon, Al, Fe and Mn were possible normalisers. Based on PCB/normaliser ratio and 95% prediction limits of scatter plots between total PCB and normaliser, all mangrove sites were not seriously contaminated by human activities. The estimated total PCBs concentrations (quantified by Congener-specific method) for most sediment ranged from 0.5 to 5.8 ng g(-1) (dry weight, n = 92). However, very high concentrations of PCB were found in sub-samples from Yi O, Tolo Pond and Lai Chi Wo, suggesting that these samples represented the PCB contaminated "hot spots".     

Determination of polychlorobiphenyl congeners (PCBs) in the surface water of the Venice lagoon

The purpose of this study is to evaluate the degree of PCB contamination of Venice lagoon water. The PCB determination was made on the filtrate ("dissolved PCBs") and on the particulate collected on the filters ("particulate PCBs") by continuous liquid-liquid extraction and sonication, respectively, and by HRGC-LRMS analysis. An estimation of the procedural and "working" blanks was also made. Water samples were collected at six sites, selected to represent all the pollution situations present in the lagoon, and at a site in the Adriatic Sea. The range of the total sum ("dissolved plus particulate") of 49 congener concentrations falls between 355 and 1868 pgl(-1); the "dissolved" fraction concentrations (250-792 pgl(-1)) are greater at six sites than that of the "particulate" fraction (105-1273 pgl(-1)). Chemometric analyses suggest that the PCB congener pattern in the Venice Lagoon is different from that in the Adriatic Sea.     

Application of AMD to the Determination of Crop Protection Agents in Drinking Water. Part IV: Fundamentals of a Confirmatory Test

A method is described for the determination of fifteen active ingredients of plant protecting products in ground-, raw, and drinking water. After extraction and enrichment of the pesticides from the water sample with solid-phase extraction, the extract is fractionated on silica-coated TLC plates, first in a so-called screening gradient by AMD (automated multiple development). The detection of the pesticides is performed by UV multidetection. Positive results from the first separation are confirmed by a second separation on silica in an AMD gradient of distinctly different selectivity, compared to the first separation. Following this strategy, it is possible to distinguish nearly all nonvolatile, from water extractable, active ingredients of plant protecting products in the market. UV spectra are taken for further confirmation of positive results. In most cases, this is possible even at the limit of determination. All chromatograms and spectra shown are raw data, resulting from the confirmatory test DIN 38407 part 11, in the laboratory of one participant*). The method is standardized in the meantime as DIN V 38407-11.     

POPs in edible clams from different Italian and European markets and possible human health risk

Human intake of persistent organic pollutants (POPs) occurs primarily through diet and fish and other seafood represent the principal means of contamination. Despite this, few legal limits have been established to protect human health from the various chemicals that are alleged to be carcinogenic or endocrine disruptor compounds.Several pools of edible clams (Tapes philippinarum and Venus gallina) bought in different Italian and European markets were examined in order to perform a risk assessment of some of these contaminants and also to identify possible health issues. POP concentrations in the soft tissues of mollusks varied considerably among source farming sites, particularly in the Venice Lagoon. Some POPs (DDTs, HCB and HCHs) showed very low concentrations and no risk for human health, in line with the limits established by European law. In contrast, PAHs could represent a potential hazard for human health and PCB levels in the most contaminated sites reached or even exceed the Minimal Risk Level as set by the ATSDR for human consumption, even if all the samples did not exceed the PCB limits in edible seafood as set by the FDA.     

Role of suspended sediments on the distribution of PCB in the Seine Estuary (France)

PCB (polychlorinated biphenyls) contamination and its relationship to SPM (suspended particulate material) have been studied in the Seine Estuary, which is heavily polluted by these persistent and hydrophobic man-made chemicals. Two sampling cruises have been performed during different freshwater discharge conditions. PCB and SPM concentrations, as well as grain-size distributions in the particulate material have been determined. Water samples have been collected at fixed positions during a tidal cycle, and along transects within the estuary.PCB concentrations vary from 2 ng 1⁻¹ in the marine zone to 250 ng 1⁻¹ within the estuary, and reach 1.3 × 10³ ng 1⁻¹ in the turbidity maximum zone. During a tidal cycle, low PCB concentrations are observed at high water, and are in the same range in February as in July. High PCB contamination is observed at low water, but PCB concentrations are about five times higher in February. SPM and PCB variations are well correlated in both periods of observations. Higher PCB contamination during February is explained by higher SPM inputs, mainly due to particles of riverine origin. The transport of PCB within the estuary depends on the quantity and the grainsize composition of suspended material, which varies according to freshwater discharge and tidal amplitude.     

Polybrominated diphenyl ethers and polychlorinated biphenyls in sediments of southwest Taiwan: regional characteristics and potential sources

Very little information is available on the contamination of coastal sediments of Taiwan by PBDEs and PCBs. In this study, we determined the concentrations of 19 PBDE and 209 PCB congeners in 57 surface sediment samples to identify the possible sources of PBDEs and PCBs. The total PBDE and PCB concentrations ranged from below detection limit to 7.73 ng/g and 0.88-7.13 ng/g, respectively; these values are within the ranges observed for most coastal sediments worldwide. The PBDE congeners were dominated by BDE-209 (50.7-99.7%), with minor contributions from penta- and octa-BDEs. The signatures of PCB congeners suggested that PCB residues in Kaohsiung coast may be the legacy of past use or the result of ongoing inputs from the maintenance, repair and salvage of old ships. Principal component analysis of the congener-specific composition of PBDEs and PCBs revealed distinct regional patterns that are related to the use of commercial products.     

Characterization and composition of heavy metals and persistent organic pollutants in water and estuarine sediments from Gao-ping River, Taiwan

The objective of this study was to determine the concentrations and possible sources of heavy metals and persistent organic pollutants (POPs) in water and estuarine sediments from Gao-ping River in order to evaluate the environmental quality of aquatic system in southern Taiwan. High concentrations of heavy metals including Cr, Zn, Ni, Cu and As, ranging from 10.7 to 180 mg/kg-dry weight (dw), were detected in sediments from Gao-ping River. When normalized to the principal component analysis (PCA), swinery and electroplating wastewaters were found to be the most important pollution sources for heavy metals. Of various organochlorine pesticide (OCP) residues detected, aldrin and total-hexachlorocyclohexane (HCH) were frequently found in sediments. The total concentrations of OCPs were in the range 0.47-47.4 ng/g-dw. Also, the total-HCH, total-cyclodiene, and total-dichlorodiphenyltrichloroethane (DDT) were in the range 0.37-36.3, 0.21-19.0, and 0.44-1.88 ng/g-dw, respectively. The polychlorinated biphenyl (PCB) concentrations in sediments from Gao-ping River ranged between 0.37 and 5.89 ng/g-dw. The PCB concentrations are positively correlated to the organic contents of the sediment particles. alpha-HCH was found to be the dominant compound of HCH in the sediments, showing that long-range transport may be the possible source for the contamination of HCH in sediments from Gao-ping River. In summary, trace amounts of POPs in estuarine sediments from Gao-ping River were detected, showing that there still exist a wide variety of POP residues in the river sediments in Taiwan. These POP residues may be mainly from long-range transport and weathered agricultural soils, while heavy metal contamination is primarily from the swinery and industrial wastewaters.     

Pestizidbestimmung im Wasser – gegenwärtige Möglichkeiten und künftige Entwicklungen

Summary: In the drinking-water regulation of the Federal Republic of Germany limit values in the range of 0.1 μg/l are established for pesticides. Identification and quantitative determination of pesticides in this concentration range require a very high expenditure concerning analysis, devices and equipment, analytical methods having been available so far only on a limited scale. The sum limit value of 0.5 μg/l pesticides may create special difficulties. In general, in view of the approx. 300 possible substances first of all a screening has to be proposed concerning the exceeding of limit values based on knowledge from the catchment area and its potential loading as the first step of investigation. Suitable methods of determination are partly available in gas chromatography and high-pressure liquid chromatography. Promising in the future development are the biochemical methods of enzyme inhibition (cholinesterase) and of immunoassay with radioactive and enzyme labelling. Nevertheless, for the foreseeable future standard methods will be available only for approx. Two thirds of the total of 300 substances, so that discussing the effectiveness of the limit values should be carried on.     

Characterization and composition of heavy metals and persistent organic pollutants in water and estuarine sediments from Gao-ping River,Taiwan

The objective of this study was to determine the concentrations and possible sources of heavy metals and persistent organic pollutants (POPs) in water and estuarine sediments from Gao-ping River in order to evaluate the environmental quality of aquatic system in southern Taiwan. High concentrations of heavy metals including Cr, Zn, Ni, Cu and As, ranging from 10.7 to 180 mg/kg-dry weight (dw), were detected in sediments from Gao-ping River. When normalized to the principal component analysis (PCA), swinery and electroplating wastewaters were found to be the most important pollution sources for heavy metals. Of various organochlorine pesticide (OCP) residues detected, aldrin and total-hexachlorocyclohexane (HCH) were frequently found in sediments. The total concentrations of OCPs were in the range 0.47–47.4 ng/g-dw. Also, the total-HCH, total-cyclodiene, and total-dichlorodiphenyltrichloroethane (DDT) were in the range 0.37–36.3, 0.21–19.0, and 0.44–1.88 ng/g-dw, respectively. The polychlorinated biphenyl (PCB) concentrations in sediments from Gao-ping River ranged between 0.37 and 5.89 ng/g-dw. The PCB concentrations are positively correlated to the organic contents of the sediment particles. α-HCH was found to be the dominant compound of HCH in the sediments, showing that long-range transport may be the possible source for the contamination of HCH in sediments from Gao-ping River. In summary, trace amounts of POPs in estuarine sediments from Gao-ping River were detected, showing that there still exist a wide variety of POP residues in the river sediments in Taiwan. These POP residues may be mainly from long-range transport and weathered agricultural soils, while heavy metal contamination is primarily from the swinery and industrial wastewaters.     

Analysis of Pulp Mill EOP Bleaching Process Effluent by Thin-layer Chromatography with Automated Multiple Development (AMD-HPTLC)

High-performance thin-layer chromatography with automated multiple development (AMD-HPTLC) was applied for the examination of pulp mill bleachery effluents from an alkali-oxygen-peroxide (EOP) bleaching stage of a sulfite pulp. A gradient based on methanol and dichloro-methane was developed for the separation of the effluent compounds over a wide range of migration distances. A series of reference substances such as lignin phenols and other aromatic acids, aldehydes, and alcohols as well as two resin acids were investigated in parallel using the AMD-HPTLC method. Characterization of the effluent compounds was possible using the migration distances and the recorded spectra. The composition of different samples of effluent were found to be very similar. The application of the AMD-HPTLC to effluent fractions from acidic liquid-liquid extraction using diethyl ether and from RP C18 solid-phase extraction allowed us to follow the behaviour of the effluent compounds in the extraction procedure.     

Trends of persistent organic pollutants in the suspended matter of the River Rhine

Recently amended European (EU) water policies call for an adequate monitoring of the chemical status of sediments and suspended matter (SM) in rivers. In this study, we focus on long‐term time series of particle‐bound hexachlorobenzene (HCB) and selected polychlorinated biphenyls (PCB‐138 and PCB‐153) that were monitored biweekly to monthly at eight stations in the River Rhine catchment. Our aims are (1) to detect trends in the concentration series HCB, PCB‐138 and PCB‐153, (2) to estimate the uncertainty of loads caused by SM collection techniques and load calculation procedures and (3) to detect trends in the subsequently calculated annual load series. HCB concentration in the SM for the period 1995–2008 significantly (p < 0·01) decreased at six of the eight monitoring stations. Decreasing PCB‐138 and PCB‐153 concentrations are significant at six of the eight and seven of the eight monitoring stations, respectively. A two‐way analysis of variance (ANOVA) that tested the effect of two collection techniques and four load calculation procedures on annual loads indicates homogeneity of the methods at four of the five monitoring stations. At Weil, only the loads of HCB, PCB‐138 and PCB‐153 are significantly affected by the collection technique. The trend analysis of an extended series (1985–2007) of annual HCB loads at Koblenz showed a significant decrease from about 110 kg year^?1 to about 15–23 kg year^?1; however, in the shorter period (1995–2007) only at two of the eight monitoring stations decreasing trends of annual contaminant load could be detected. We conclude that any of the tested load calculation procedures can be applied, as loads do no differ systematically. Although a high uncertainty in load estimation exists (e.g. maximum percentage error of E = [18·1, 122·5]% for HCB), the monitoring programme at the Rhine is adequate for analysing the long‐term chemical status of SM. Copyright © 2011 John Wiley & Sons, Ltd.     

Determination of nitrophenols,diaminotoluenes, and chloroaromatics in ammunition wastewater

Methods for the determination of three compound classes, i. e. diaminotoluenes, nitrophenols, and chloroaromatics in groundwater of a former ammunition plant are reported. Diaminotoluenes were extracted by discontinuous liquid/liquid-, nitrophenols by continuous liquid/liquid-extraction using dichloromethane, and chloroaromatics by solid-phase extraction. These compound classes may be analyzed by gas chromatography (GC) or gas chromatography coupled to mass spectrometry (GC/MS) without derivatization or after derivatization with N-methyl-bis(trifluoroacetamide) (MBTFA) or heptafluorobutyric anhydride (HFBA) in the case of diaminotoluenes and HFBA or acetic anhydride in the case of nitrophenols. An atomic emission detector (AED) coupled to a gas chromatograph may be employed for the analysis of chloroaromatics. High selectivity can be achieved using the characteristic wavelengths of chlorine. A variety of these compounds were identified and quantified in a groundwater sample from the former ammunition plant Elsnig (Saxony, Germany). Concentrations were in the lower ppb range. Thus, dichlorobenzenes which may have been used as substituents at the end of World War II could be identified in groundwater samples at this site.     

PCDD/Fs and PCBs in seafood species from Moreton Bay, Queensland, Australia

Previous studies have identified elevated levels of polychlorinated dibenzo-p-dioxins (PCDDs) in sediments and megafauna (dugongs and green turtles) in the marine environment of southeast Queensland, Australia. Little information exists, however, regarding the levels of PCDDs, polychlorinated dibenzofurans (PCDFs) and related polychlorinated biphenyls (PCBs) in seafood from this area. This study aims to establish baseline information on PCDD/F and PCB contamination in a range of seafood species from Moreton Bay and to investigate contaminant variability due to harvesting season, size, habitat location and trophic level. In addition, different seafood extraction methods were tested to evaluate their impact on lipid yields and contaminant concentration. Overall, the median TEQ(DF&PCB) levels in seafood from Moreton Bay were elevated compared to background levels in Australian marine/estuarine and retail fish. However, TEQ(DF&PCB) levels of most seafood analysed were below the respective EU maximum limits. High inter- and intraspecies variability was observed, which could be partially attributed to differences in trophic level, season harvested and habitat location.     

Determination of Chloroethers in Aqueous Samples Using Solid-phase Microextraction

A method for the determination of di- and tetrachlorinated ethers (haloethers) in aqueous samples using solid-phase microextraction (SPME) combined with capillary GC has been developed. Using 100-μm polydimethylsiloxane fibers, the influence of several parameters on the SPME procedure like the exposure time of the fiber in the aqueous sample, the desorption temperature, and the salt content of the sample have been studied. Salt addition has a strong effect on the extraction efficiency of the haloethers investigated. Working with saturated salt solutions, the factor increase of the peak areas was in the range from 5 to 12. These improvements are accompanied by decreased precision and increased equilibration times. The SPME method combined with several detectors (FID, ECD, MS in SIM mode) was evaluated with respect to detection limits, linearities, and precisions. Working with salt addition and FID, detection limits of all compounds investigated were in the range of 0.3 to 1.2 μg/L. Using ECD, the LOD values (limits of detection) were only improved for the tetrachlorinated bis(propyl) ethers (<10 ng/L). Employing mass-spectrometric detection in SIM mode for all chlorinated ethers, detection limits lower than 100 ng/L could be reached. Working with saturated salt solutions, the coefficients of variation were <9% RSD. However, without salt addition, the precision is better than 2.5% RSD for all analytes. Investigations showed that the analysis of the haloethers with SPME is not influenced significantly by the matrix Elbe water. The results of two series of samples demonstrate that SPME-GC-MS allows the sensitive determination of the di- and tetrahalogenated ethers in Elbe river water.     

Residues and sources recognition of polychlorinated biphenyls in surface sediments of Jiaojiang Estuary, East China Sea

Twenty-three surface sediment samples were collected from Jiaojiang Estuary, East China Sea in order to assess the distribution, possible sources, and potential risk of polychlorinated biphenyls (PCBs) in the environment. Total concentrations of PCBs ranged from 4.93 to 108.79 ng g(-1) dry weight for all sampling stations, with a substantial higher concentration in the inner part of the estuary than the outer part of the estuary. PCB patterns in sediments from sites 1-8 were extremely dominated by tetra-PCBs, which probably due to the discharge of local industrial plants but not the expected input from the nearby e-waste recycling areas. Principal component analysis revealed that the sources of PCBs for sites 9-23 were associated with Aroclor 1248 or Aroclor 1221. However, physical migration and bio-degradation may also play a role on PCB distribution. Hazard assessment of PCBs indicated possible toxic potential, particularly in areas close to point sources.     

Spatial patterns in PCBs, pesticides, mercury and cadmium in the common sole in the NW Mediterranean Sea, and a novel use of contaminants as biomarkers

We assessed spatial patterns in 37 PCB congeners, eight pesticides, and the heavy metals mercury and cadmium in the flatfish Solea solea at four sites in the Gulf of Lions (NW Mediterranean). Overall contaminant concentrations generally exceeded those reported for S. solea elsewhere, but fell into the range of other Gulf fishes, testifying of a relatively high contaminant load of this area. Spatial patterns in all three contaminant classes were highly significant, but differed among classes. PCB congener and chlorination class profiles also differed among sites. The observed patterns would be consistent with (1) PCB point-sources in the Eastern Gulf (Marseille, Rhone River) versus dominance of atmospheric input in the West, (2) pesticide input by the Rhone and from agricultural fields in the West, and (3) mercury point-sources near Marseille. The unique, site-specific contaminant profiles prove to be a powerful tool to differentiate between S. solea populations from different sites.     

PCB concentrations and metabolism patterns in common terns (Sterna hirundo) from different breeding colonies in The Netherlands

PCB levels in blood of common terns (Sterna hirundo) from Terneuzen, a breeding colony in The Netherlands with relatively low breeding success, were significantly higher than in birds from two Dutch reference colonies, one nearby (Oesterdam) and one further away (the Isle of Griend). However, a detailed analysis of the patterns of PCB congeners in birds from the different colonies indicated that birds from Terneuzen and to a lesser extent birds from the Oesterdam showed Ah-receptor mediated activity of P450 iso-enzymes. It is concluded that the induction of this enzyme activity in Terneuzen may be related to PCBs as well as other non-identified compounds. In contrast to this, it is likely that at the Oesterdam non-identified compounds are mainly responsible for the enzyme activity, resulting in a shift of PCB congener patterns.     

The influence of the color of visibility targets on the visibility

Reduced visibilities have been simulated in the laboratory by means of a hydrosol. It was illuminated homogeneously by iodine quartz lamps producing an illuminance similar to a bright day. In the hydrosol several visibility targets were suspended at different distances and the visibility observation was performed by counting the number of visible objects. By this method a very accurate and fast determination of the visibility was possible. The extinction coefficient of the hydrosol was determined with a long path photometer: the intrinsic brightness of the objects in the illuminated hydrosol was determined for several wavelengths by means of a fiber optic. The correlation between the measured visibility and the extinction coefficient shows that the frequently used visual range underestimates the visibility, since the highest perception for an atmospheric aerosol is not at 550 nm but at 580 nm wavelength. Therefore it is suggested to use the atmospheric extinction coefficient at 580 nm for the calculation of the visual range. All colored objects could be seen less far, since they had a smaller contrast at the wavelength of maximum perception than the black object. Dark colored objects can be seen further than bright ones. Especially objects that have a high reflection in the yellow and organe have a small visibility. If the intrinsic brightness of the objects and the extinction coefficient (both as a function of wavelength) are known, the wavelength of maximum perception can be calculated and from this the visibility. The visibility thus calculated agrees with the observed visibility. If visibility observations in the atmosphere have to be performed with non-black objects, methods for corrections to the visibilty of a black object are given.