Effect-based assessment of passive air samples from four countries in Eastern Europe

Although passive sampling has been previously used for the monitoring of volatile and semi-volatile contaminants in air, there are limited data on the use of this technique coupled with bioassays based on specific biological responses. Biological responses including those mediated by the aryl hydrocarbon (AhR) receptor as well as (anti-)estrogenicity and (anti-)androgenicity of samples from four Eastern European countries (Lithuania, Slovakia, Romania, and Serbia) were determined. To address the potential differences of specific toxic potencies of pollutant mixtures in ambient air in Eastern Europe, each country was characterized by a single more remote location that served to determine regional background conditions and one location in more urbanized and industrialized locations, which were defined as “impacted” areas. Besides samples from Lithuania, a significant gradient in concentrations of AhR-mediated potency from background and impacted localities was observed. Greatest potencies were measured in samples from impacted locations in Romania and Slovakia. Concentrations of polycyclic aromatic hydrocarbons (PAHs) that were quantified accounted for 3–33 % of the 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents determined by use of the bioassay. No significant estrogenic potency was detected but anti-estrogenic effects were produced by air from two background locations (Lithuania, Slovakia) and three impacted locations (Lithuania, Romania, and Serbia). Anti-androgenic potency was observed in all samples. The greatest anti-estrogenic potency was observed at the background location in Slovakia. Anti-estrogenic and anti-androgenic potencies of studied air samples were probably associated with compounds that are not routinely monitored. The study documents suitability of passive air sampling for the assessment of specific toxic potencies of ambient air pollutants.     

Analysis of per- and polyfluorinated alkyl substances in air samples from Northwest Europe

Air samples were collected from 4 field sites in Europe: 2 sites from the UK, Hazelrigg (semi-rural) and Manchester (urban); 1 site from Ireland: Mace Head (rural); and 1 site from Norway: Kjeller (rural). Additionally, air samples were taken from indoor locations in Troms?, Norway. Air samples were collected using high-volume air samplers employing sampling modules containing glass-fibre filters (GFFs, particle phase), and glass columns with a polyurethane foam (PUF)-XAD-2-PUF sandwich (gaseous phase). Typical outdoor air volumes required for the determination of per- and polyfluorinated alkyl substances (PFAS) ranged from 500-1800 m3. GFFs and PUF-XAD columns were analysed separately to obtain information on phase partitioning. All air samples were analysed for volatile, neutral PFAS, with selected GFF samples halved for analysis of both neutral and airborne particle-bound ionic PFAS. Volatile PFAS were extracted from air samples by cold-column immersion with ethyl acetate, and were analysed by gas chromatography-mass spectrometry in the positive chemical ionisation mode (GC-PCI-MS). Ionic PFAS were extracted from GFFs by sonication in methanol, and were analysed by liquid chromatography-time-of-flight-mass spectrometry (LC-TOF-MS) using electrospray ionisation in the negative ion mode (ESI-). Perfluorooctanoate (PFOA) was often the predominant analyte found in the particulate phase at concentrations ranging from 1-818 pg m(-3), and 8:2 fluorotelomer alcohol (FTOH) and 6:2 FTOH were the prevailing analytes found in the gas phase, at 5-243 pg m(-3) and 5-189 pg m(-3), respectively. These three PFAS were ubiquitous in air samples. Many other PFAS, both neutral and ionic, were also present, and levels of individual analytes were in the 1-125 pg m(-3) range. Levels of some PFAS exceeded those of traditional persistent organic pollutants (POPs). In this study, the presence of 12:2 FTOH and fluorotelomer olefins (FTolefins), and ionic PFAS other than perfluorooctane sulfonate (PFOS) and PFOA, are reported in air samples for the first time. Concentrations of neutral PFAS were several orders of magnitude higher in indoor air than outdoor air, making homes a likely important diffuse source of PFAS to the atmosphere. Our repeated findings of non-volatile ionic PFAS in air samples raises the possibility that they might directly undergo significant atmospheric transport on particles away from source regions, and more atmospheric measurements of ionic PFAS are strongly recommended.     

Simultaneous quantification of Bi(III) and U(VI) in environmental water samples with a complicated matrix containing organic compounds

Trace amounts of bismuth(III) and uranium(VI) can be simultaneously determined in a single scan by adsorptive cathodic stripping voltammetry in the presence of cupferron as a complexing agent. Optimal conditions were found to be: 0.1 mol?L^?1 acetate buffer (pH 5.3), 5?×?10^?5?mol?L^?1 cupferron, accumulation potential of ?0.25 V, and accumulation time of 30 s. The linear range of Bi(III) and U(VI) was observed over the concentration range from 2?×?10^?9 to 2?×?10^?7?mol?L^?1 and from 1?×?10^?8 to 5?×?10^?7?mol?L^?1, respectively. The influence of the main components of real water samples such as foreign ions and organic substances (surface active substances, humic substances) was precisely investigated. The method was applied to the simultaneous measurements of bismuth and uranium in natural water samples.     

Study of heavy metals in some environmental samples

Fuels like coal and rubber are frequently used for brick burning. However, both coal and rubber contain heavy metals. These heavy metals may elutriate in the wake of fly ash or may adsorb or absorb in the product. The present work deals with the analysis of heavy metals in some samples collected from brick burning industries located in the vicinity of a metropolitan city, Peshawar, Pakistan. Samples from raw clay, product, chimney scale and fossil fuel & rubber were collected and leached with acid mixture. The leachates were concentrated and analyzed by atomic absorption spectrophotometer for the determination of chromium (Cr), lead (Pb), cadmium (Cd) and antimony (Sb). It was observed that heavy metals are present in clay, brick and chimney scale. However, significant amount of these metals was observed in chimney scale. It is inferred that such emanations laden with heavy metals are accompanying the stack gases which are being dumped in to the environment. In order to avoid environmental problems, strict environmental regulations shall be enforced and a constant check on these emanations to the environment must be made to ensure clean air act.     

A rapid extractive spectrophotometric determination of copper(II) in environmental samples, alloys, complexes and pharmaceutical samples using 4-N,N(dimethyl)amino]benzaldehyde thiosemicarbazone

Composite samples of septage discharging at the Khirbit As-Samra municipal wastewater treatment plant were analyzed during the period from February to the end of October 2007. Septage showed difference in concentrations of pollutants between summer and winter. The average total chemical oxygen demand (COD) of 6,425 mg/L during summer was 2.16 times greater than that in winter, which is 2,969 mg/L. The total biochemical oxygen demand (5 d) represented 45% of total COD in both winter and summer. Anaerobic biodegradability was 75% after 81 d of digestion at 35°C with a biodegradation rate constant (k) of 0.024 d^???1, which was lower compared with 0.103 d^???1 calculated for wastewater with domestic origin in Jordan. Aerobic biodegradability for septage was 48%??COD basis??after 7 d of digestion at 35°C. The lower anaerobic biodegradation rate of septage compared with that of raw wastewater of domestic origin suggested that septage could have a negative effect on the performance of a domestic wastewater treatment plant if septage discharges are not taken into account in the original design of the treatment plant.     

Methodologies for determination of antimony in terrestrial environmental samples

Methodologies for the environmental analysis of total antimony and aqueous chemical speciation are critically reviewed, including preparation techniques for aqueous and solid matrices and the determination of solid state partitioning and recommendations are given for future research directions. Concentrations of total antimony commonly present in aqueous and solid environmental samples are readily determined using present day analytical techniques. This has resulted primarily from technological advances in microwave digestion for solid matrices and the development of plasma based analyte detection systems. ICP-AES and ICP-MS techniques are both utilised for the environmental analysis of total antimony concentrations. However, ICP-MS is increasingly favoured as a result of reduced spectral interferences and the potential for analyte detection in the pg mL(-1) range. Determination of aqueous antimony speciation presents a number of complex analytical challenges and highly selective separation and identification techniques are required prior to detection. The majority of published techniques including common applications of hydride generation are insufficiently selective for the determination of intrinsic chemical speciation and often only oxidation state data are obtained. The recent in-line applications of HPLC-ICP-MS offer the potential for highly selective separations of aqueous antimony species and determination of detailed chemical speciation data. However, considerable development work is required to optimise chromatographic separations and identify uncharacterised species resident in environmental systems. Analytical techniques to aid the determination of antimony's associations with solid environmental matrices include the application of chemical extraction procedures and leaching experiments. To date, this area of analytical research has received little attention and further studies are required to elucidate this aspect of antimony's environmental chemistry.     

A highly sensitive spectrophotometric determination of micro amounts of vanadium(V) in environmental and alloy samples by using 3,4-dihydroxybenzaldehydeisonicotinoylhydrazone (3,4-DHBINH)

3, 4-Dihydroxybenzaldehydeisonicotinoylhydrazone was prepared, characterized with spectral analyses and used for developing a new method for the simple, sensitive and rapid spectrophotometric determination of vanadium(V) which gives maximum absorbance at wave length 360 nm. The metal ion gives a yellow colored complex with 3, 4-DHBINH in acetate buffer of pH 5.5 with 1:1 (metal:ligand) composition. The method obeys Beer's law in the range 0.5-5.3 mug mL(-1) of vanadium(V). The molar absorptivity and Sandell's sensitivity were found to be 1.29 x 10(4) L mol(-1) cm(-1) and 0.003949 mug cm(-2) respectively. The correlation co-efficient of the V(V)-3, 4-DHBINH complex was 0.992 which indicated an excellent linearity between the two variables. The repeatability of the method was checked by finding the relative standard deviation (RSD) as 0.424% (n = 5), and its detection limit 0.01677 mug mL(-1) of vanadium(V). The instability constant of the method was calculated by Asmus' method as 4.1666 x 10(-3). The interfering effect of various cations and anions were also studied. The proposed method was successfully applied to the determination of vanadium(V) in environmental samples (water and soil) tobacco leaves and alloy samples. The validity of the method was tested by comparing the results with those obtained using an atomic absorption spectrophotometer.     

Synthetic musks in environmental samples: indicator compounds with relevant properties for environmental monitoring

Synthetic musks (nitro and polycyclic musks) are a group of chemicals offering a wide range of important properties for environmental monitoring programs. They are produced as odorous chemicals and added to a wide variety of perfumes, toiletry products and other household products. As such, they are directly applied in cosmetic products or in washed textiles to the human body in considerable concentrations and accumulate owing to dermal resorption. In addition, synthetic musks also enter the environment via waste water treatment. Several polycyclic musks are chiral. By using chiral gas chromatographic methods, it is possible to determine the enantiomeric ratio and assess their bioavailability. Although an comprehensive quality assurance program must be followed during the analysis of synthetic musks in environmental samples, the determination of these compounds is not very demanding and can be carried out by a standard analytical laboratory specialising in trace analysis of organic pollutants. Owing to the pheromone-like behavior of some synthetic musks, the induction of receptors in olfactory systems should be investigated. For HHCB (1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta[g]-2-benzopyran, e.g., Galaxolide), three-dimensional structural similarities with androstenone (5 alpha-androst-16-en-3-one), a mammalian steroid pheromone, were found, which support the hypothesis of HHCB as an artificial pheromone. Owing to their environmental abundance, their relation to human activities and their potential for pheromone-like environmental behavior, synthetic musks are especially valuable as future indicator chemicals for environmental monitoring.     

Stability and storage problems in organotin speciation in environmental samples

The stability of both tributyltin (TBT) and triphenyltin (TPT) in water, sediment, oysters and cockles was studied over a period of 18 months using several storage conditions. Butyltins were stable in unacidified sea-water stored in polycarbonate bottles in the dark at 4 degrees C for 7 months, but half of the TBT concentration was lost after 540 d. A comparable preservation time was achieved for butyltins stored on C18 cartridges at room temperature. However, phenyltins extracted from sea-water were stable for only 60 d stored on cartridges and even more pronounced losses (about 90% after 540 d) occurred when they were stored in either polycarbonate or Pyrex glass bottles. Losses of organotins were observed in sediments after air drying and pasteurization treatments using a freeze-dried sediment as a comparator, whereas both butyltin and phenyltin species remained stable in sediments stored at -20 degrees C for the 18 months tested, irrespective of the treatment used for stabilization. Air drying followed by pasteurization was shown to be superior to other treatments for the stabilization of organotin compounds in sediments stored at higher temperatures, but 30% of TBT was lost after 540 d at 25 degrees C. Finally, butyltins were stable in both frozen cockles and oysters in the dark over a 7 month period and in freeze-dried samples stored at 4 degrees C for 5 months, but TBT losses of about 70% were observed after 540 d.     

Chemical sequential extraction for metal partitioning in environmental solid samples

A comprehensive review of the sequential extraction schemes for metal fractionation in environmental samples (ie., sediment, soil, sewage sludge, fly ash, etc.) is presented. The review contains more than 400 references and covers principally the literature published over the last decade. The use of each reagent involved in these schemes is looked at critically, and guidelines for their selectivity and extraction capacity are given. The operational character of these schemes is emphasised. Topics such as comparability between sequential extraction schemes of widespread use, harmonisation, acceleration, validation, etc. are addressed and future developments outlined.     

The distribution of organic matter in songkhla lake basin (SLB)

The concentrations and the distribution of organic matter in SLB (e.g. the outer part of Thale Sap Songkhla area) were examined during the period of September 1988 to September 1989. Organic matter in water samples were analyzed by gravimetry. Total organic matter and dissolved organic matter concentrations ranged from 74 to 7908 mg/L and from 23 to 7813 mg/L, respectively. Except for a set of observations which showed low concentrations during the flood season in November 1988, organic matter was regularly distributed throughout SLB. Domestic effluent and aquaculture are hypothesized as major sources of organic matter contamination. The levels of organic matter concentrations in SLB are significantly higher than would be expected for an area considered to be uncontaminated. The data also indicated a linear relationship between concentrations of suspended organic matter and suspended solids. This may be due to the organic matter associated with suspended solids.     

The lognormal distribution,environmental data,and radiological monitoring

The lognormal distribution has become a common choice to represent intrinsically positive and often highly skewed environmental data in statistical analysis. However the implications of its use are often not carefully considered. With an emphasis on radiological monitoring applications, this paper reviews what assuming lognormality means in terms of data analysis and interpretation. The relationship of using normal theory methods on log transformed data to multiplicative errors and hypothesis testing in the original scale is also discussed.Work performed under the auspices of the U.S. Department of Energy, DOE Contract No. DE-AC-07-76ID01570.     

Environmental levels of Linear alkylbenzene Sulfonates (LAS) in sediments from the Tagus estuary (Portugal): environmental implications

Sediments from the Tagus estuary (Portugal) were collected at 40 stations in July and December 2004. Total LAS concentrations ranged between 0.03 and 17.76 mg LAS.kg(-1) dry weight in July, and between 0.09 and 9.57 mg LAS.kg(-1) in December. Highest LAS concentrations were found at the upper northern part of the estuary, coincident with the localisation of an important waste water treatment station. According to the Predicted No Effect Concentration (PNEC) of 8.1 mg.kg(-1) derived for this compound, Environmental Risk Assessment (ERA) identified a hazard for the ecosystem at the station with the highest LAS concentration, and similar results are obtained by Equilibrium Partitioning Method (EPM). Nevertheless, LAS concentrations decreased significantly between samplings in the stations with the highest LAS concentrations in July, whereas increased LAS concentrations at adjacent stations were found in December. In the remaining stations, LAS concentrations were up to three orders of magnitude lower, representing no hazard for the sediment community.     

The determination and distribution of Zn in surface water samples collected in the northeast Atlantic Ocean

Dissolved Zn concentrations were determined in surface water samples collected on-line along transects in the eastern North Atlantic in spring (March 1998). Two frontal zones could be identified in the research area by a change in salinity, temperature and nutrient concentrations. One zone was identified at 42 degrees N, separating the North Atlantic central water (NACW) and the Atlantic surface water (ASW) from each other, and another one crossing the continental slope at 12 degrees and 8 degrees E, respectively. Variability in Zn concentrations was observed near these zones, not only as a result of a change of water mass, but also due to external Zn sources. Surface Zn concentrations were 0.5-1 nM and 2 nM in the NACW and ASW, respectively, increasing to 4 nM over the continental shelf and finally 5-6 nM in the English Channel. Contributions of Zn derived from shelf sediments appear to be the major source for the enriched surface values in the continental zone.     

Spectrophotometric determination of platinum(IV) in alloys, complexes, environmental, and pharmaceutical samples using 4-[N,N-(diethyl)amino] benzaldehyde thiosemicarbazone

4-[N,N-(Diethyl)amino] benzaldehyde thiosemicarbazone (DEABT) is proposed as an analytical reagent for the spectrophotometric determination of platinum(IV). The DEABT forms 1:2 yellow complex with Pt(IV), which is sparingly soluble in water and completely soluble in water–ethanol–DMF medium. The Pt(IV)–DEABT complex shows maximum absorbance at 405 nm. Beer’s law is valid up to 7.80 μg cm^???3, and optimum concentration range for the determination of platinum(IV) is 0.48–7.02 μg cm^???3. The molar absorptivity and Sandell’s sensitivity of the method are found to be 1.755 × 10⁴ dm³ mol^???1 cm^???1 and 0.0012 μg cm^???2, respectively. The relative error and coefficient of variation (n?=?6) for the method does not exceed ±0.43% and 0.35%, respectively. Since the method tolerates a number of metal ions commonly associated with platinum, it can be employed for the determination of platinum in environmental samples, pharmaceutical samples, alloys, catalysts, and complexes. The method is rapid as the Pt(IV)–DEABT complex is soluble in water–ethanol–DMF medium and not requiring any time consuming extraction method for the complex.     

The prevalence of bacterial resistance in clinical, food, water and some environmental samples in Southwest Nigeria

The resistance pattern and mechanisms of bacterial isolates obtained from clinical origin, soil, industrial effluent, orange juice products and drinking water were studied using commonly used antibiotics. The microbial load of the water samples, industrial effluent and orange juice products were 1.0 × 10¹–2.25 × 10⁶, 2.15 × 10⁵, and 3.5 × 10⁴–2.15 × 10⁵ cfu mL^–1, respectively. The faecal coliform test revealed that only two out of twenty orange juice products had MPN of 2 and 20, the MPN of water ranged from 1–1800, while the effluent had MPN of 1800. The bacterial isolates that were isolated include E. coli, S. aureus, P. vulgaris, S. marcescens, S. pyogenes, B. cereus, B. subtilis, Micrococcus sp., Klebsiella sp., P. aeruginosa, and Enterobacter sp. Also, clinical and soil isolates of P. aeruginosa were used in the study. Among the eight antibiotics tested for resistance on five strains of each bacterium, seven different resistance patterns were observed among the bacterial isolates obtained from water, effluent and orange juice products. Among the clinical and soil isolates of P. aeruginosa, four multiple-drug resistance patterns were obtained. Thirty strains of E. coli and S. aureus were tested for -lactamase production and fourteen strains, seven each of E. coli and S. aureus that had high Minimum Inhibitory Concentration values (MIC) for both Amoxycillin and Cloxacillin were positive.     

Colloidal mercury (Hg) distribution in soil samples by sedimentation field-flow fractionation coupled to mercury cold vapour generation atomic absorption spectroscopy

Diverse analytical techniques are available to determine the particle size distribution of potentially toxic elements in matrices of environmental interest such as soil, sediments, freshwater and groundwater. However, a single technique is often not exhaustive enough to determine both particle size distribution and element concentration. In the present work, the investigation of mercury in soil samples collected from a polluted industrial site was performed by using a new analytical approach which makes use of sedimentation field-flow fractionation (SdFFF) coupled to cold vapour generation electrothermal atomic absorption spectroscopy (CV-ETAAS). The Hg concentration in the SdFFF fractions revealed a broad distribution from about 0.1 to 1 μm, roughly following the particle size distributions, presenting a maximum at about 400-700 nm in diameter. A correlation between the concentration of Hg in the colloidal fraction and organic matter (O.M.) content in the soil samples was also found. However, this correlation is less likely to be related to Hg sorption to soil O.M. but rather to the presence of colloidal mercuric sulfide particles whose size is probably controlled by the occurrence of dissolved O.M. The presence of O.M. could have prevented the aggregation of smaller particles, leading to an accumulation of mercuric sulfides in the colloidal fraction. In this respect, particle size distribution of soil samples can help to understand the role played by colloidal particles in mobilising mercury (also as insoluble compounds) and provide a significant contribution in determining the environmental impact of this toxic element.     

Factor analysis of trace-element data from tree-bark samples in The Netherlands

Monte Carlo-assisted factor analysis has been applied to a data set of 20 trace-element concentrations in tree-bark samples obtained from 123 locations in The Netherlands, with the aim to investigate the suitability of bark as a biomonitor for air pollution. A Monte Carlo approach was used to give more insight to the uncertainties and significance levels of the factor analysis results. Notwith-standing a rather strong influence of soil material on the concentration levels, factor analysis enabled the identification of five significant pollution source types, all of which corresponded with source types found in an earlier biomonitoring study in The Netherlands using epiphytic lichens. A more detailed comparison with the lichen results showed a remarkable difference in lead concentrations between bark and lichen. It was concluded that bark can be successfully employed as a biomonitor for air pollution. The power of factor analysis to adequately determine the soil contribution may render extensive sample washing procedures superfluous.     

Monoclonal antibody-based broad-specificity immunoassay for monitoring organophosphorus pesticides in environmental water samples

The development of easy-to-use and rapid-monitoring immunoassay methods for organic environmental pollutants in a class-selective manner is a topic of considerable environmental interest. In this work, a heterologous competitive indirect enzyme-linked immunosorbent assay (ciELISA) based on a monoclonal antibody (MAb) with broad-specificity for organophosphorus pesticides (OPs) was applied to the detection of O,O-diethyl and O,O-dimethyl OPs in water samples. The ciELISA conditions were carefully optimized to obtain a three to five-fold improvement of sensitivity for most OPs, and thirteen OPs were determined at concentrations ranging from 0.017 to 30 ng mL(-1). The determination of spiked environmental water samples showed average recoveries from 81.5% to 115.1%, with the coefficient of variation (CV) ranging from 6.1% to 20.9%, which showed satisfactory reproducibility of the developed ciELISA. To overcome the negative aspect of broad-specificity immunoassays not providing qualitative and quantitative analysis of individual OPs in blind samples, we used "percent inhibition rate" to make the developed ciELISA a semi-quantitative method, which allows the monitoring of positive samples from hundreds of negative samples. The determination of OPs in blind water samples by the developed ELISA with confirmation by HPLC-MS/MS analysis demonstrated that the assay is ideally suited as a screening method for OP residues prior to chromatographic analysis.