Congener group patterns of chloroparaffins in marine sediments obtained by chloride attachment chemical ionization and electron capture negative ionization

Congener group patterns of technical short chain and medium chain chloroparaffins (SCCP and MCCP) were determined by electron capture negative ionization (ECNI) and chloride attachment chemical ionization (CACI) mass spectrometry (MS). In contrast to CACI-MS, congener patterns obtained by ECNI showed always a shift to the next higher chlorinated congener and carbon chain length group. Consequently, the calculated molecular masses and chlorine contents were higher for ECNI (factor 1.10+/-0.03 and 1.09+/-0.03, respectively). ECNI/CACI ratios in sediment samples from the North and Baltic Sea were also slightly higher. However, a more pronounced shift of the congener pattern for a given carbon chain length to congeners with 2-3 more chlorine atoms was observed. SCCP and MCCP concentrations obtained by ECNI-MS were in the range of 8-63ngg(-1) (North Sea) and 22-149ngg(-1) dry weight (Baltic Sea). MCCP levels were highest in all samples (MCCP/SCCP factor 1.1-3.2).     

First study of congener group patterns and concentrations of short- and medium-chain chlorinated paraffins in fish from the North and Baltic Sea

This study presents the first investigation of concentrations and congener group patterns of short- (SCCPs) and medium-chain chlorinated paraffins (MCCPs) in fish from the North and Baltic Sea. North Sea dab, cod and flounder were studied. High resolution gas chromatography (HRGC) coupled to low resolution mass spectrometry (LRMS) in the electron capture negative ionization mode (ECNI) was employed. Good linearity (R2>0.993, 7 measuring points) was achieved between 1 and 100 ng/g of CP mixtures for SCCPs and MCCPs. The limits of detection were 0.5-1 ng/microl of CP mixture for the major congener groups of SCCPs and MCCPs. A clean-up comprising fat extraction, adsorption chromatography on silicagel impregnated with concentrated sulphuric acid and adsorption chromatography on Florisil was employed to avoid interferences from other polychlorinated compounds. Recoveries of CPs in spiked samples ranged between 80% and 100%. Accuracy was controlled with spiked samples and deviated not more than 10% from the expected values. Quantification was performed with standards of an average chlorine content as close as possible to that of the samples (SCCPs: 59-62%, MCCPs: 53-58%). SCCP concentrations ranged between 19 and 286 ng/g liver wet weight (ww), MCCP concentrations were comparable with a range of 25-260 ng/gww. Congener group patterns were also determined and discussed. In samples from the Baltic Sea the SCCP congener pattern was similar to that of commercial SCCP mixtures or C13 congeners were most abundant. In samples from the North Sea a higher relative abundance of C10 congeners was observed.     

Simultaneous monitoring of profiles of polycyclic aromatic hydrocarbons in contaminated air with semipermeable membrane devices and spruce needles

Gaseous emissions of combusted electronic scrap, PVC, carpet and wood were monitored for polycyclic aromatic hydrocarbons (PAHs) by simultaneous use of semipermeable membrane devices (SPMDs) and shoots of spruce needles (Picea abies). It was found that phenanthrene, acenaphthylene and fluorene were the dominating PAHs in all samples. SPMDs and needles mainly sequestered PAH associated with the vapor phase. Particle-bound PAHs were only detected in small amounts, at which the needles tended to uptake more of these compounds in comparison to the SPMDs. Nevertheless, the logarithm of the concentrations of PAHs analyzed in both passive samplers after the same sampling period exhibited a significant linear correlation with correlation coefficients larger than 0.8073. SPMDs and spruce needles can complement each other in passive air sampling for compounds with a preference to the gas phase rather than aerosols.     

Pine needles as passive bio-samplers to determine polybrominated diphenyl ethers

Eight polybrominated diphenyl ethers (PBDEs) were determined in pine needles of three species (Pinus halepensis, Pinus pinea and Pinus nigra) collected in the NE Spain in an attempt to use this matrix for the biomonitoring of airborne PBDEs. The method used was based in ultrasonic extraction followed by alumina and Florisil clean-up and determination by gas chromatography coupled to mass spectrometry in negative chemical ionization. Recoveries were between 99% and 138%, limits of detection between 0.011 and 0.070 ng g⁻¹-dw (0.232 ng g⁻¹-dw for BDE 209) and repeatability lower than 13%. PBDE levels ranged between 0.027 ng g⁻¹-dw and 13.04 ng g⁻¹-dw, with predominance of BDE 209, followed by BDEs 47. P. halepensis was the species with the highest PBDE levels and P. nigra, the least, according to their widespread and remote distribution, respectively. The presence of PBDEs in pine needles was attributed to the release of in-use PBDEs, transport through atmosphere and adsorption upon lipid rich pine needles. Given the easy collection of pine needles, its ample distribution and its potential to accumulate airborne contaminants, this matrix is proposed as passive bio-sampler to be used in PBDE monitoring programs.

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Pine needles can be used to biomonitor airborne PBDEs.     

Can pine needles indicate trends in the air pollution levels at remote sites?

Data from ten years of integrated monitoring were used here to evaluate whether pine needles are a feasible tool for an assessment of long-term trends of the atmospheric contamination. Pine needles collected once a year were compared to high volume air samples collected for 24 h, every 7 days, and passive air samples integrated over 28-day periods. Results showed the same concentration patterns of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) captured in needles and high volume samples. Passive air samplers were less efficient in sampling the particle-bound compounds. Theoretical air volume equivalent to each needle sample (V_EQ) was calculated as a ratio of the needle concentration over the mean air concentration. Results indicated different equivalent volumes for PAHs and organochlorines, possibly due to the faster degradation rates of PAHs in needles. The most important finding is that in the long term a needle monitoring gives very similar information on temporal trends of the atmospheric pollution as does a high volume air monitoring.     

The impact of ambient ozone on mountain spruce forests in the Czech Republic as indicated by malondialdehyde

Malondialdehyde (MDA), a product of lipid peroxidation and biomarker of oxidative stress, is measured over the long term in spruce Picea abies needles under real conditions in three Czech mountain border areas. The trends presented collate the MDA content in spruce needles with ambient ozone, temperature and precipitation as casual, and defoliation as a subsequent factor for the period 1994-2006. We have found the overall decreasing trends in MDA and defoliation. The highest MDA and defoliation are recorded in the Jizerske, the lowest in the Krusne hory Mts. Out of the examined variables the MDA is predicted best by mean temperature in vegetation season, median of O₃ concentrations and AOT40; these three variables account for 34% of MDA1 and 36% of MDA2 variability. Our hypothesis that higher ambient O₃ exposure results in higher MDA contents in P. abies needles under real conditions has not been approved.     

Simultaneous monitoring of PCDD/Fs and PCBs in contaminated air with semipermeable membrane devices and fresh spruce needles

The contaminated air with burning plastic floor and electronic scrap was monitored with semipermeable membrane devices (SPMDs) and fresh unpolluted spruce needles at the same time for polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs). It was found that there were more polychlorinated dibenzofurans (PCDFs) than polychlorinated dibenzo-p-dioxins (PCDDs) collected from contaminated air. The total amounts of PCBs were much higher than that of PCDD/Fs, but the contribution of them to the WHO-TEQ was less than that of PCDD/Fs. Triolein-containing SPMDs can absorb much more PCDD/Fs and PCBs than spruce needles when they were exposed in contaminated air simultaneously. The logarithm of the concentrations of PCDD/Fs and PCBs in SPMDs and in spruce needles at the same sampling time exhibited a significant linear correlation, the correlation coefficients were larger than 0.86 for PCDD/Fs and 0.92 for PCBs. SPMDs and spruce needles are effective passive air sampler for PCDD/Fs and PCBs. SPMDs and spruce needles can complement each other in passive air sampling.     

Conifer needles as passive biomonitors of the spatial and temporal distribution of DDT from a point source

Needles of two conifer species, Picea abies and Pinus nigra, were used as passive samplers for monitoring air contamination by sampling at increasing distances from a suspected point source of DDT. Needle concentrations declined with increasing distance downwind of the point source allowing to identify spatial and temporal trends of accumulation. This suggested that conifer needles are effective biomonitors of contamination levels in areas characterized by the presence of semi-volatile substances. Differences in uptake were apparent between the species. Needle morphology and structure were studied with scanning electron microscope (SEM) as were dimensional parameters (surface area, volume). The results suggest that the concentrations depend on a mechanism involving the inner structure of the needles, specifically the number and accessibility of resin channels rather than their surface area. Pine needles have more channels with greater accessibility than spruce. The results suggest that spruce is more suitable for short term measurement while pine for determining long term cumulative exposure.     

Deposition of semivolatile organic compounds to spruce needles

The deposition of atmospheric tetrachlorobenzene, pentachlorobenzene, hexachlorobenzene, α-HCH, γ-HCH, DDT, DDE and the PCB congeners 52, 101, 138, 153 and 180 to spruce needles (Picea abies) was estimated for a period of 9 months. Accumulation in spruce as a result of dry gaseous deposition, particle bound deposition and wet deposition was calculated on the basis of the corresponding deposition rates and the compounds’ concentrations in the different atmospheric compartments. The comparison of the calculated values with the concentrations of the compounds measured in 9-month-old spruce needles showed that for many compounds each deposition pathway could explain a large part of the concentrations found in the needles.     

Uptake,translocation and fate of trichloroacetic acid in a Norway spruce/soil system

Trichloroacetic acid (TCA) is a secondary atmospheric pollutant formed by photooxidation of chlorinated solvents in the troposphere--it has, however, recently been ranked among natural organohalogens. Its herbicidal properties might be one of the factors adversely affecting forest health. TCA accumulates rapidly in conifer needles and influences the detoxification capacity in the trees. The aim of the investigations--a survey of which is briefly given here--was to elucidate the uptake, distribution and fate of TCA in Norway spruce. For this purpose young nursery-grown plants of Norway spruce (Picea abies (L.) Karst.) were exposed to [1,2-14C]TCA and the fate of the compound was followed in needles, wood, roots, soil and air with appropriate radio-indicator methods. As shown by radioactivity monitoring, the uptake of TCA from soil by roots proceeded most rapidly into current needles at the beginning of the TCA treatment and was redistributed at later dates so that TCA content in older needles increased. The only product of TCA metabolism/biodegradation found in the plant/soil-system was CO(2) (and corresponding assimilates). TCA biodegradation in soil depends on TCA concentration, soil humidity and other factors.     

Indication of airborne pollution by birch and spruce in the vicinity of copper smelter

The aim of the study was determination of air pollution impact of the copper smelter in Bor and its surroundings (Serbia) by assessing the suitability of birch (Betula pendula Roth.) and spruce (Picea abies L.) for the purposes of biomonitoring and comparing it with previously published data from the same study area. The concentrations of Cu, Zn, Pb and Mn in leaves/needles, branches, roots and soil were determined. Sampling was performed during 2009 in two zones with high load of air pollution due to copper mining and smelting activities, and one background zone. Metal accumulation and translocation was evaluated in terms of biological factors. In addition, plant enrichment factor was calculated. According to the results, plant foliage was not enriched through soil, which indicates absorption from the air, with both species acting as excluders of Cu, Pb, Zn and Mn. Leaves were more enriched with all the metals than needles, indicating a better response of birch to airborne pollution than spruce. Cluster analysis showed different level of pollution at the sites, while correlations between Cu and Pb obtained by Principal Component Analysis indicated their anthropogenic origin. Regarding previously published results, beside birch leaves, pine needles (which showed higher level of response to pollution compared to linden leaves) could be applied in air biomonitoring surveys near copper smelters.     

Analysis of chlorinated paraffins in cutting fluids and sealing materials by carbon skeleton reaction gas chromatography

Chlorinated paraffins (CPs) pose a major risk in the environment, due to their wide application, to their persistence, to their carcinogenic potential, and in view of the fact, that they cannot be easily identified. Various commercial cutting fluids and sealing materials were analysed for CPs with carbon skeleton reaction gas chromatography (GC) and flame ionization detection. CPs are simultaneously dechlorinated and hydrogenated to the corresponding alkanes with Pd catalyst material in the GC injector. With this method, the carbon chain length of commercial technical CPs was determined. In six of sixteen sealing materials we found five short and one medium chain length polychlorinated paraffins in percentages of 9-16% (w/w). In five cutting fluids we found predominantly medium to long chain length chloroparaffins with percentages of 2.5-31% (w/w), only one fluid contained short chain CPs.     

Haloacetic acids,phytotoxic secondary air pollutants

Haloacetic acids are atmospheric oxidation products of airborne C₂-halocarbons which are important solvents and propellants. Levels of trichloroacetate (TCA) in conifer needles from mountain ranges in Germany (Black Forest, Erzgebirge) and from two sites in Finland are compared; TCA is present in conifer needles at concentrations up to 0.7 μmol/kg, MCA up to 0.2 μmol/kg. At the Finnish sites, TCA-concentrations and branch degeneration symptoms of Scots pine are correlated. Monochloroacetate (MCA) has been determined in needle samples from Southern Germany in concentrations exceeding its phytotoxicity threshold towards photoautotrophic organisms. Data on atmospheric chloroacetate levels in Germany are also given; ambient air levels of chloroacetic acids range from about 2 pmol/m³ (TCA) to 390 pmol/m³ (MCA). TCA and dichloroacetic acid (DCA) arise from atmospheric oxidation of airborne C₂-chlorocarbons, while the source of MCA is not yet known; several tentative pathways are suggested.     

Biomonitoring of polychlorinated biphenyls in Bavaria/Germany—long-term observations and standardization

In the 1980s, it was demonstrated that semi-volatile organic compounds (SVOCs) like polychlorinated biphenyls (PCBs) accumulate in plant leaves. Plants are at the base of the food chain, and therefore a starting point for transfer of PCBs to animals and related human exposure. For two decades, the Environment Agency of the German federal state of Bavaria (LfU) has been operating long-term monitoring stations to measure the impact of organic air pollutants. Standardized ryegrass, curly kale, and spruce needles are used as bioindicators for the atmospheric entries of PCBs into vegetation. From the end of 1990s to 2009, there was a marked decline in the concentrations of indicator PCBs (i-PCBs) and a minor decline in PCB-TEQ levels. After 2009, the concentrations leveled off. In rural areas, the median concentrations of Σ6 i-PCB in ryegrass and curly kale were about 3 and 4 μg/kg dm in 2000, and have been about 0.5 and 1 μg/kg dm since 2009, respectively. Concentrations in spruce needles fell from 0.9 to 0.4 μg/kg dm. Median PCB-TEQ concentrations in the bioindicator plants ranged from 0.05 to 0.23 ng/kg dm between 2002 and 2009 and from 0.15 to 0.05 ng/kg dm after 2009. Indicator PCB and PCB-TEQ concentrations were several times higher at the urban station in Munich than at the rural areas, reflecting the emissions from in-use PCB stocks in the building sector. The likely reason of the slower decrease of PCB-TEQ compared to i-PCBs is the formation of PCB-126 by dechlorination of industrial PCBs in open applications.     

Thermal degradation products of spruce needles

Spruce needles are analysed by in-source pyrolysis (Py)-field ionization (FI) mass spectrography and Curie-point Py-gas chromatography/electron ionization mass spectrometry. The identified thermal degradation products allow the interpretation of the FI mass signals. It could be shown that Py-FI mass spectra of plant materials are representative fingerprints which consist primarily of molecular ions of Py products derived from the thermal degradation of the main constituents of spruce needles such as carbohydrates, lignin, lipids and proteins. Primary building blocks of these biopolymers form characteristic Py products of spruce needles. Furthermore, over 500 different molecular ion species of volatilized, thermostable plant constituents are recorded using FI as soft ionization method. The present study shows that Py-FIMS is suitable for the rapid and comprehensive characterization of complex biological materials, without pretreatment of the sample except of drying and milling. The presented results contribute to the basic knowledge for the evaluation of the causes of the present tree damage.     

Short-chain chlorinated paraffins (SCCPs) in surface soil from a background area in China: occurrence, distribution, and congener profiles

Short-chain chlorinated paraffins (SCCPs) are extremely complex technical mixtures of polychlorinated n-alkanes with carbon chain lengths from C₁₀ to C₁₃ and chlorine content between 49 and 70 %. SCCPs are under consideration for inclusion in the Stockholm Convention on persistent organic pollutants. SCCPs have been used extensively in industrial production, but little is known about the pollution level in soil environment in China. In this study, levels and distribution of SCCPs in soil samples from Chongming Island were analyzed. Concentrations of total SCCPs in soil samples ranged from 0.42 to 420 ng?g^?1, with a median of 9.6 ng?g^?1. The ubiquitous occurrence of SCCPs in Chongming Island implied that long-range atmospheric transport and soil–air exchange may be the most important pathways for SCCP contamination in the background area. The localized SCCP contamination could be derived from an unidentified source. Hierarchical cluster analysis indicated that C₁₃- and C₁₁-congeners were predominant in most soils and C₁₀- and C₁₂-congeners dominated in the remaining soils. Cl₇- and Cl₈-congeners were on the average the most dominant chlorine congeners in nearly all soils. Principal component analysis suggested that the separation of even and odd carbon chain congeners occurred during long-range atmospheric transport and aging in soil in the study area.     

Assessing the genotoxicity of urban air pollutants using two in situ plant bioassays

Genotoxicity of urban air has been analysed almost exclusively in airborne particulates. We monitored the genotoxic effects of airborne pollutants in the urban air of Perugia (Central Italy). Two plant bioindicators with different genetic endpoints were used: micronuclei in meiotic pollen mother cells using Tradescantia-micronucleus bioassay (Trad-MCN) and DNA damage in nuclei of Nicotiana tabacum leaves using comet assay (Nicotiana-comet). Buds of Tradescantia clone # 4430 and young N. tabacum cv. Xanthi plants were exposed for 24 h at three sites with different pollution levels. One control site (indoor control) was also used. The two bioassays showed different sensitivities toward urban pollutants: Trad-MCN assay was the most sensitive, but DNA damage in N. tabacum showed a better correlation with the pollutant concentrations. In situ biomonitoring of airborne genotoxins using higher plants combined with chemical analysis is thus recommended for characterizing genotoxicity of urban air.     

Biomonitoring airborne parent and alkylated three-ring PAHs in the Greater Cologne Conurbation I: Temporal accumulation patterns

Polycyclic aromatic hydrocarbons (PAHs) comprise an important group of air pollutants, with three-ring components (PAH-3) often dominating. Spatiotemporal variation in atmospheric PAH-3 can be analyzed by biomonitoring but high vapour pressure and low octanol-air-partitioning of PAH-3 cause dynamic accumulation on plant surfaces. This study for the first time shows that PAH-3 exhibit systematic accumulation trends on pine needles of 3-48 months of exposure time at six sites in Germany. Correlation of needle exposure time with PAH-3 concentration was r² = 0.83 for phenanthrene and methylphenanthrenes, r² = 0.77 for cyclopenta[def]phenanthrene, r² = 0.60 for dibenzothiophene, r² = 0.57 for dimethylphenanthrenes and r² = 0.32 for retene. Variations in PAH-3 for summer and winter collected needles emphasize vegetation-air-partitioning influence on cumulative PAH-3 loads. PAH-3 ratios calculated for needle cohorts indicate persistence of original PAH patterns thus demonstrating the source-diagnostic potential of pine needle biomonitoring, which is utilized in part II of this study where spatial distribution of PAH-3 is investigated and related to emission sources.     

Photolytic clean-up of biological samples for gas chromatographic analysis of chlorinated paraffins

A method based on gas chromatography electron capture detection (GC-ECD) for the analysis of chlorinated paraffins (CPs) in biological samples has been investigated. The method includes photolytic destruction of halogenated aromatic compounds, such as PCBs, to eliminate some of the interferences in the analysis of CPs in environmental samples. Gel permeation chromatography was used to isolate CPs from the interfering components of Toxaphene and chlordane after the photolysis. GC-ECD gave a detection limit of 20 ng CPs/g fresh muscle tissue. The recovery of CPs from a spiked moose liver sample was estimated to 94%.