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1.
Pentachlorophenol (PCP) has been used as a herbicide, biocide and preservative worldwide since the 1930s and as a result, extensive and prolonged contamination exists. The environmental impact increases when its many degradation products are taken into consideration. A number of chloroanisols and their related chlorophenols have been found in cork slabs collected from Portuguese oak tree forests before stopper manufacturing, and contamination by PCP and polychlorinated anisole (PCA) has been detected in Canadian forests. It is suggested that the use of polychlorinated phenols, in particular PCP, is thought to be a cause of the cork taint problem in wine, a major socio-economic impact not only for industry but on sensitive and highly biodiverse ecosystems. It also highlights particular issues relating to the regional regulation of potentially toxic chemicals and global economics world wide. To fully understand the impact of contamination sources, the mechanisms responsible for the fate and transport of PCP and its degradation products and assessment of their environmental behaviour is required. This review looks at the current state of knowledge of soil sorption, fate and bioavailability and identifies the challenges of degradation product identification and the contradictory evidence from field and laboratory observations. The need for a systematic evaluation of PCP contamination in relation to cork forest ecosystems and transfer of PCP between trophic levels is emphasised by discrepancies in bioaccumulation and toxicity. This is essential to enable long term management of not only transboundary contaminants, but also the sustainable management of socially and economically important forest ecosystems.  相似文献   

2.
A stream of substrate pentachlorophenol [PCP, 5 mg min(-1) in water-methanol (1 + 4, v/v)] was merged with 1.5 ml min(-1) of supercritical carbon dioxide (scCO2) and delivered to a reactor column (25 cm x 1 cm) of zero-valent palladium-magnesium mixture. The resulting dechlorinations, although very efficient, were not quantitative. For continuous operation at 400 degrees C for 6 h, phenol was the principal product, with lesser quantities of methylated products and only traces of chlorinated products (principally monochlorinated species). PCP deoxygenation was not observed and ring methylation was decreased relative to analogous reactions in hydroxylic organic solvent. With time, the reactor column slowly lost dechlorination activity. Reducing the loading of Pd0 on Mg0 from 2% to 1% (w/w) apparently did not change the course of the reaction; however, the dechlorination capacity was decreased correspondingly. None the less, over 6 h or 5 h of continued operation, the dechlorination efficiency was 0.995 for the 2% (w/w) loading of Pd0 on Mg0 and 0.984 for the 1% (w/w) loading.  相似文献   

3.
The surface microlayer often contains pesticides at levels which may be more than one hundred thousand times those sampled in the remainder of the water column. Standard bioassay systems cannot asses these pesticides since no system yet devised has made use of organisms inhabiting the surface microlayer. Using floating propagules of Pseudoaegerita matsushimae, an aeroaquatic hyphomycetous fungus, a bioassay system was devised in which the percentage germinations of such propagules after exposure to various levels of pesticides were plotted to produce a dosegermination scale onto which subsequent data could be fitted. The following pesticides and pesticide mixtures were used: PCP; DDT; Methoxychlor; Bis(tributyl)tin Oxide; Malathion; Captan; 1 part PCP/1 part DDT; 2 parts PCP/1 part DDT; 3 parts PCP/1 part DDT; 2 parts DDT/1 part PCP; 3 parts DDT/1 part PCP; 1 part PCP/1 part Methoxychlor; 2 parts PCP/1 part Methoxychlor; 3 parts PCP/1 part Methoxychlor; 2 parts Methoxychlor/1 part PCP; 3 parts Methoxychlor/1 part PCP. The bioassay system revealed increased sensitivity to pesticides and pesticide mixtures which affected respiratory metabolism. Some pesticide mixtures were more effective in inhibiting germination than their individual components while others appeared much less toxic to the propagules than their unassisted components.  相似文献   

4.
A trace analytical method is presented for the analysis of hydroxylated polychlorinated biphenyl metabolites (HO-PCBs) and pentachlorophenol (PCP) in human plasma. The described methodology is a modification of a previously validated method used for PCB and organochlorine pesticide analysis. The modified method enables the combined analysis of phenolic and neutral halogenated compounds. A tandem Florisil column is used for separating the HO-PCBs and PCP from the neutral fraction, instead of the more common chemical partitioning. In the same step the neutral fraction is purified for GC analysis. The extraction of the HO-PCBs and PCP was found to be highly dependent on sufficient acidification of the sample and the polarity of the extracting solvent. Analysis of plasma samples gave recovery rates for (13)C(6)-PCP and (13)C(12)-4-HO-CB 187 of 64 and 72%, respectively. The limit of detection ranged between 2-20 pg g(-1) plasma for the HO-PCBs and 5 pg g(-1) plasma for PCP. No matrix interferences were observed in the chromatograms. In plasma samples (n = 15) from the native Chukchi people in Uelen (Russian Arctic), a population with high PCB exposure, the median ratio of sum HO-PCBs to sum PCBs was as high as 0.4 and the sum HO-PCBs and PCBs were significantly correlated (r(2) > 0.7, p < 0.01). The median sum HO-PCBs (10 congeners) was 5920 pg g(-1) plasma with 4-HO-CB 107 as the dominating congener (median: 1670 pg g(-1) plasma). The median PCP level was measured at 642 pg g(-1) plasma.  相似文献   

5.
In order to be able to make a decision, as to whether a room or building has a health-endangering pentachlorophenol (PCP) concentration, usually the PCP concentrations in air and settled dust are measured. The variability of the PCP concentration in indoor air and dust was studied. Air and dust samples were taken from 75 rooms in 30 buildings with suspicion of application of PCP-containing wood preservatives. Sampling was repeated four times within 18 months. Thirty-six rooms were reconstructed within the study; 39 rooms had unchanged contamination status during the study. The four times repeated measurements of PCP concentrations in air and dust in these rooms showed large variations of the measured values. The variability of the results is to a large extent in the same range as the measured values. The observed relative standard deviation of the PCP concentrations in air and dust does not depend on the average PCP concentration detected in the individual rooms.  相似文献   

6.
毛细管柱气相色谱法测定水质五氯酚   总被引:2,自引:0,他引:2  
用乙酸酐衍生,正己烷液一液萃取,毛细管柱气相色谱-电子捕获检测器对地表水、废水中五氯酚进行了测定,确定五氯酚浓度范围在5.0—500μg/L之间时,样品的测定精度、回收率及方法检出限均能满足要求。  相似文献   

7.
The feasibility of the Hofmann clathrates Ni(CN)2(NH3)·G(G=guest molecule) and the octahedral Werner-type complexes Ni(X)2(L)4 (X=NCS, NCO, CH3CO2, C6H5CO2; L=Py, 4-Mepy) as a scavenger for organic substrates in a polluted aqueous or organic medium is dependent on the complex lability, thermal stability and reversibility in solvent trapping which can be conveniently studied by thermogravimetric means. Besides the parent monomeric octahedral complexes, all the thermal decompositional intermediates, namely, monomeric tetrahedral, dimeric octahedral and polymeric octahedral, are also potential scavengers for selected organic substances though they operate via a cycle of bond-making and bond-breaking processes.  相似文献   

8.
Two PCP-degrading bacterial strains, Bacillus cereus (ITRC-S6) and Serratia marcescens (ITRC-S7) were used for the treatment of pulp and paper mill effluent at conditions; 1.0% glucose and 0.5% peptone at 30 +/- 1 degrees C at 120 rpm for 168 h of incubation. These two bacterial strains effectively reduced colour (45-52%), lignin (30-42%), BOD (40-70%), COD (50-60%), total phenol (32-40%) and PCP (85-90%) within 168 h of incubation. However, the highest reduction in colour (62%), lignin (54%), BOD (70%), COD (90%), total phenol (90%) and PCP (100%) was recorded by mixed culture treatment. The bacterial mechanism for the degradation of pulp and paper mill effluent may be explained by an increase in the cells biomass using added co-substrates resulting liberation of significant amount of chloride due to bacterial dechlorination of chlorolignins and chlorophenols this showed reduction in colour, lignin and toxicity in the effluent. Further, GC-MS analysis of ethyl acetate-extractable compounds from treated pulp paper mill effluent reinforces the bacterium capability for the degradation of lignin and pentachlorophenol, as many aromatic compounds such as 2-chlorophenol, 2, 4, 6-trichlorophenol and tetrachlorohydroquinone, 6-chlorohydroxyquinol and tetrachlorohydroquinone detected which were not present in the untreated effluent.  相似文献   

9.
During 24 h, water samples were taken for determination of a number of key parameters in a water system containing high concentrations of FeII at circumneutral pH. None of the major constituents (Ca, Mg, Na, K and sulfate) showed diurnal variations, while dissolved oxygen and pH increased during the night. This increase could entirely be explained by the decrease in water temperature. However, the concentration of FeII slightly increased at constant concentration of total Fe during the night, opposite to earlier observations in other systems where the presence of FeII was shown to be controlled by photoreduction. Nocturnal peaks of FeII have also been observed in other systems with high iron concentrations, however, at acidic pH, but without obvious explanation. The mechanisms for this process therefore need further investigation.  相似文献   

10.
毛细管气相色谱法测定鳌江表层沉积物中五氯酚和六氯苯   总被引:3,自引:0,他引:3  
建立了超声波萃取-醋酸酐原位衍生化-毛细管气相色谱同时测定鳌江表层沉积物中五氯酚和六氯苯的方法,优化了试验条件。方法线性范围为5μg/L-200μg/L,五氯酚和六氯苯的检出限均为0.5ng/g,沉积物标准物质的测定值符合质控要求,基质加标的平均回收率分别为77.7%和81.8%。  相似文献   

11.
The toxicity of single and combined mixtures of 2,4-dichlorophenol (2,4-DCP), 2,4,6-trichlorophenol (2,4,6-TCP), and pentachlorophenol (PCP) to Daphnia magna was studied. The toxicity ranking of these three single chlorophenols (CPs) to Daphnia magna was PCP > 2,4-DCP > 2,4,6-TCP. The toxic units (TU) approach was used to estimate the combined effects in experiments, the median effective concentration (EC(50)) values were 0.87-1.21 and 0.46-0.59 for binary and ternary mixtures, respectively. Response surface models of General Linear Models (R(2) > 0.90, residual deviation < 3.25) were established for all three binary mixtures. The toxicity for ternary mixtures based on the EC(50)-value and 10% effective concentration (EC(10))-value fixed mixture ratio presented a synergism. The risk based on the single CP's toxicity test may be underestimated. In addition, four approaches (concentration addition, toxicity equivalency factors, effect summation, and independent action) were used for the calculation of combined effects of the mixture. The experimental results showed that concentration addition and toxicity equivalency factor approaches were effective methods for calculation of additive effects of mixtures from binary systems of CPs; while independent action and effect summation (low simulated tail) predicted lower toxicity than experimental results. Limitations of the traditional focus on the effects of single agents were highlighted; hazard assessments ignoring the possibility of joint action of CPs will almost certainly lead to significant underestimations of risk.  相似文献   

12.
One hundred and fourteen surface sediments were collected from the Maozhou River Watershed in Shenzhen, China from December 2009 to January 2010. Three individual chlorinated polycyclic aromatic hydrocarbons (ClPAHs), six individual brominated polycyclic aromatic hydrocarbons (BrPAHs), and five corresponding parent polycyclic aromatic hydrocarbons (PAHs) were determined. The concentration of 9-chlorophenanthrene was the highest ranging from 0.51-289 ng g(-1) (average, 16.5 ng g(-1)). For BrPAHs, the concentration of 2-bromofluorene was the highest ranging from 0.31-266 ng g(-1) (average, 35.3 ng g(-1)). No correlation was observed between the concentrations of ClPAHs and parent PAHs in surface sediments. In addition, there was no correlation between 1-bromopyrene, 7-bromobenz(a)anthracene and 9,10-dibromoanthracene, and corresponding parent PAHs. However, a significant correlation was found between 9-bromophenanthrene and phenanthrene (p < 0.01), between 9-bromoanthracene and anthracene (p < 0.05), and between 2-bromofluorene and fluorene (p < 0.05). Six fly ash samples collected from one of the municipal domestic waste incineration plants in Shenzhen were also analyzed for source identification. The concentration of 7-bromobenz(a)anthracene was the highest, ranging from 3.21-4.08 ng g(-1). In addition, 2-bromofluorene was not detected in all the fly ash samples. No correlation was found between the concentrations of Cl-/BrPAHs and corresponding parent PAHs in fly ashes. We also examined the relationship between the levels of Cl-/BrPAHs in surface sediments and the urbanization process. Our results suggested the levels of individual Cl-/BrPAHs congeners presented a similar increasing trend with the increasing urbanization level.  相似文献   

13.
The distribution and composition of hydrocarbons in sediment from the Fladen Ground oilfield in the northern North Sea have been investigated. The total PAH concentrations (2- to 6-ring parent and alkylated PAHs, including the 16 US EPA PAHs) in sediments were relatively low (<100 microg kg(-1) dry weight). The PAH, the Forties crude and diesel oil equivalent concentrations were generally higher in sediment of fine grain size and higher organic carbon concentration. PAH distributions and concentration ratios indicated a predominantly pyrolytic input, being dominated by the heavier, more persistent, 5- and 6-ring compounds, and with a high proportion of parent PAHs. The n-alkane profiles of a number of the sediments contained small, high boiling point, UCMs, indicative of weathered oil arising from a limited petrogenic input. The geochemical biomarker profiles of the sediments that contained UCMs showed a small bisnorhopane peak and a high proportion of norhopane relative to hopane, indicating that there was contamination from both Middle Eastern and North Sea oils. Therefore contamination was not directly as a result of oil exploration activity in the area. The most likely source of petrogenic contamination was from general shipping activity.  相似文献   

14.
Off-line solid-phase extraction (SPE) combined with liquid chromatography-electrospray tandem mass spectrometry (LC-ESI-MS-MS) was used to study the estuarine behaviour of the polar pesticides, atrazine, chloridazon, diuron and metolachlor, and their transformation products (TPs), hydroxyatrazine (HA), desisopropylatrazine (DIA), desethylatrazine (DEA), 3,4-dichlorophenylmethylurea (DPMU) and monuron. The compounds were identified by comparing their LC retention times and product-ion spectra with those of standard solutions. In all but one case the detection limits of the method were sufficient to determine the compounds of interest over the entire salinity range in the estuary. The concentrations of the dissolved pesticides ranged from 70 ng l-1 for chloridazon to 1350 ng l-1 for diuron. The levels of TPs were 3-8% of the levels of their parent pesticide. The mixing plots of polar pesticides and their TPs indicated that TPs, which are present in fresh river water, are conservatively transported to the sea and that no additional amounts of TPs are formed during their transport through the estuary. The one exception was HA, of which approximately 10% of the amount transported to the North Sea is formed in the lower part of the estuary by photochemical oxidation of atrazine. The latter was concluded from the ratios of each analyte over the sum total of the parent pesticide and all TPs along the salinity gradient, which proved to be a useful tool for identifying such estuarine transformations.  相似文献   

15.
The problems of different mapping units which hitherto formed the basis for irrigation soil surveys of the savanna landscapes in Nigeria are discussed. Using data from a semi-detailed soil survey, the possibility of establishing the major variations in soil properties which are relevant to irrigation by using a combination of parent material and slope position as mapping units are examined. In the mapping units considered, thirteen topsoil and eleven subsoil properties are significantly different between mapping units and have smaller variances within than between the mapping units. The variations of these topsoil and subsoil properties are also adequately accounted for by using parent material/slope position as a basis for mapping, suggesting that units based on parent material/slope position are of high utility for establishing the irrigation potentials of areas at the feasibility level of survey.  相似文献   

16.
The environmental fate and movement of herbicides widely used for weed control in corn are assessed for a deep loess soil in southwestern Iowa. Beginning in the early 1980s, the herbicide-based weed control program emphasized the application of atrazine (ATR) or cyanazine (CYN) and metolachlor (MET) for both broadleaf and grass control. Between 1992 and 1995, concentrations of ATR, desethylatrazine (DEA), desisopropylatrazine (DIA), CYN and MET were measured in rainwater, both shallow and deep vadose zone water, and well water. Results show that the frequency of herbicide detections and the range and distribution of occurrences are dependent upon both landscape position and temporal inputs of recharge water from rainfall. Generally, DIA was observed more frequently and in higher mean concentration in well water than DEA, while DEA was observed more frequently than DIA in vadose zone groundwater. A chromatographic analogy is suggested to explain the occurrence patterns observed for both parent herbicide and degradation products within the unsaturated zone water. Analysis of rainwater samples collected during this time also revealed low concentrations of ATR, CYN and MET, with the timing of the detections indicative of non-local transport. Results show that the deep loess soil conducts both water and agricultural chemicals relatively rapidly and as such represents a production system which is vulnerable to contamination of shallow groundwater by herbicide-derived chemicals. Results also illustrate the importance of including major herbicide degradation products in water resource impact assessment studies.  相似文献   

17.
A tuneable, high pulse-repetition-frequency, solid state Nd:YAG pumped titanium sapphire laser capable of generating radiation for the detection of OH, HO2, NO and IO radicals in the atmosphere by laser induced fluorescence (LIF) has been developed. The integration of the laser system operating at 308 nm into a field measurement apparatus for the simultaneous detection of hydroxyl and hydroperoxy radicals is described, with detection limits of 3.1 x 10(5) molecule cm(-3) (0.012 pptv in the boundary layer) and 2.6 x 10(6) molecule cm(-3) (0.09 pptv) achieved for OH and HO2 respectively (30 s signal integration, 30 s background integration, signal-to-noise ratio = 1). The system has been field tested and offers several advantages over copper vapour laser pumped dye laser systems for the detection of atmospheric OH and HO2 radicals by LIF, with benefits of greater tuning range and ease of use coupled with reduced power consumption, instrument footprint and warm-up time. NO has been detected in the atmosphere at approximately 1 ppbv by single photon LIF using the Alpha 2Sigma+ <-- Chi 2Pi1/2 (0,0) transition at 226 nm, with absolute concentrations in good agreement with simultaneous measurements made using a chemiluminescence analyser. With some improvements in performance, particularly with regard to laser power, the theoretical detection limit for NO is projected to be approximately 2 x 10(6) molecule cm(-3) (0.08 pptv). Whilst operating at 445 nm, the laser system has been used to readily detect the IO radical in the laboratory, and although it is difficult to project the sensitivity in the field, an estimate of the detection limit is < 1 x 10(5) molecule cm(-3) (< 0.004 pptv), well below previously measured atmospheric concentrations of IO.  相似文献   

18.
A few days after the grounding of the oil tanker Braer on 5 January 1993, an Exclusion Zone was designated by Order under the Food and Environment Protection Act 1985, prohibiting the harvesting of farmed or wild shellfish within the Zone to prevent contaminated products reaching the market place. The order was progressively lifted for species that were found to be free of petrogenic taint and for which the polycyclic aromatic hydrocarbon (PAH) levels were within the range for reference samples. This Order, however, still remains in place for mussels (Mytilus edulis) as the PAH levels are higher than in reference mussels. To investigate the possible source of PAHs found in these mussels, sediments were collected from three reference and three Zone sites and their hydrocarbon compositions studied using the n-alkane composition and concentration, PAH composition and concentration and the sterane and triterpane composition. The reference site at Olna Firth was found to have the highest levels of 2-6-ring parent and branched PAHs, the highest concentration in one of the pooled sediments being 4,530 ng g(-1) dry weight. Values in the other two reference sites (Vaila Sound and Mangaster Voe) ranged from 248.7 to 902.2 ng g(-1) dry weight. PAH concentrations at the Zone sites (Sandsound Voe, Stromness Voe and Punds Voe) ranged from 641.0 to 2,766 ng g(-1) dry weight. The PAH data were normalised to the percentage of organic carbon and log-transformed prior to being analysed using principal component analysis. The mean total PAH concentrations for Zone sites were found not to be significantly different from the reference sites. The PAH concentration ratios were consistent with the main source of PAHs being pyrolysis. However, there was a petrogenic contribution, suggested by the presence of alkylated PAHs, with Punds Voe having the largest petrogenic hydrocarbon content. This was supported by the triterpane profiles and the presence of a UCM in the aliphatic chromatograms from Punds Voe sediments.  相似文献   

19.
Due to high usage of tetracycline antibiotics, concerns have been raised about their environmental fate. In this study, potential changes in the pseudo-first-order hydrolysis rate constants for three tetracyclines, tetracycline (TC), oxytetracycline (OTC) and chlortetracycline (CTC), were evaluated by measuring the rate constants in batch and column leaching experiments. The first-order hydrolysis rate constants were measured at pH 5, 7, and 9 using batch tests. The values were highest at pH 7 for all three tetracyclines (0.0030 ± 0.0004, 0.0042 ± 0.0001, and 0.0323 ± 0.0003 h(-1) for TC, OTC, and CTC, respectively), indicating relatively short environmental half-lives of tetracyclines. Interestingly, it was found that the rates of degradation of the parent tetracyclines were much faster when silica sand was present in a batch solution or when the solution was passed through a silica column. For example, the ratios of the first-order degradation rate constants obtained in the column experiments to those in batch experiments were 13.2, 2.1, and 2.0 for TC, OTC, and CTC at a volumetric flow rate of 0.08 mL h(-1), with an observed tendency for this ratio to increase with an increased flow rate. This indicates that the silica surface may serve as a catalyst for hydrolysis and that the actual environmental half-lives of tetracycline antibiotics could be shorter than those estimated from laboratory hydrolysis rate constants using the standard batch protocol. Furthermore, the toxicity of the column effluent containing hydrolysis metabolites was assessed using bioluminescence inhibition in Vibrio fischeri. It was estimated that the toxicity of the metabolites of CTC was lower than that of their parent compound, whereas the toxicity of metabolites of TC and OTC was as high as or higher than that of their parent compounds.  相似文献   

20.
A procedure to assess the bioavailability of persistent organic pollutants (POPs) from soil samples has been developed. The procedure is based on the use of simulated in vitro gastrointestinal extraction to remove POPs from soil matrices. The level of recovery, using this approach, is assessed following liquid-liquid extraction (LLE) and analysis by gas chromatography-mass selective detection (GC-MSD). The remaining soil residue is then extracted using pressurised fluid extraction (PFE) followed by GC-MSD analysis to assess the residual fraction. The residual fraction is monitored to determine the unavailable fraction i.e. not available for absorption in the gastrointestinal tract of humans. The procedure was applied to four soil samples i.e. an aged, spiked soil and three certified reference materials (CRMs) contaminated with POPs. Recoveries of pesticides (lindane, endosulfan I, endrin, DDE, DDD and endosulfan II), phenols (cresol, TCP and PCP), and base neutral compounds (hexachloroethane, acenaphthene, dibenzofuran, fluorene and hexachlorobenzene) from aged, spiked soil following extraction with gastric fluid ranged from 0.8 to 8.3% while following intestinal extraction ranged from 5.5 to 13.5%, irrespective of POP. Recoveries of pesticides (lindane, endosulfan I, endrin, DDE, DDD and endosulfan II) from CRM 805-050 following extraction with gastric fluid were below the limit of detection while following intestinal extraction ranged from 5.3 to 12.8%. Recoveries of phenols (cresol, TCP and PCP) from CRM 401-225 following extraction with gastric fluid ranged from 1.6 to 2.0% while following intestinal extraction ranged from 4.1 to 5.4%. Recoveries of base neutral acid analytes (hexachloroethane, acenaphthene, dibenzofuran, fluorene and hexachlorobenzene) from CRM 107-100 following extraction with gastric fluid ranged from 1.4 to 4.0% while following intestinal extraction ranged from 6.6 to 12.7%. It has been found that the majority of POPs present i.e. >75%, would be excreted if consumed and not be absorbed in the gastrointestinal tract of humans.  相似文献   

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