Methods comparison, transport and distribution of polar herbicides in the Baltic Sea.

Two LC-MS/MS methods including different sample preparation and quantitative processes showed a good agreement for analysis of the herbicides MCPA, mecoprop, isoproturon, bentazon and chloridazon, and the metabolite chloridazon-methyl-desphenyl (CMD) in estuarine waters. Due to different sensitivity of the methods only one could be used to analyze marine samples. The transport of these compounds to the Baltic Sea via ten German estuaries and their distribution between coastal water and sediments was studied. The results showed that all selected compounds can be transported to the Baltic Sea (0.9-747ng/L). Chloridazon, bentazon, isoproturon and CMD were detected (0.9-8.9ng/L) in the coastal waters and chloridazon and isorproturon in the sediments (5-136pg/g d.w.). Levels of contaminants in the sediments could be influenced by the total organic carbon content. Concentrations observed in the Baltic Sea are most likely not high enough to cause acute effects, but long term effect studies are strongly recommended.

Organic polar pollutants in surface waters of inland seas.

Available data about contamination by polar substances are mostly reported for rivers and near-shore waters and only limited studies exists about their occurrence in marine waters. We present concentrations and distribution of several polar pesticides and UV-filters in surface waters of three inland seas, the Baltic, Black and Mediterranean Sea. Many of the investigated compounds were below detection limits, however, those found in off-shore waters raise a concern about their persistence and possible adverse effect on the ecosystem. Despite a longstanding EU-wide ban we were able to detect atrazine in the Mediterranean and the Baltic Sea. Concentrations in the Black Sea were substantially higher. Runoff from agricultural and urban areas was the main transport route to marine ecosystems for investigated compounds, though irgarol in Mediterranean waters was attributed to intense maritime traffic. 2-Phenylbenzimidazole-5-sulfonic acid was the only UV-filter detected in marine waters, while benzophenone-4 was observed in the estuaries. Occurrence of UV-filters was seasonal.

Levels and sources of planar and non-planar PCBs in pine needles across Poland.

Under a small project, one-year-old Scots Pine needles collected from 25 spatially distant sites were examined in monitoring the extent of environmental diffusion and possible sources of polychlorinated biphenyls (PCBs) in ambient air, their depositions and uptake by plants in Poland. The congener-specific determination of planar and non-planar chlorobiphenyls was achieved by isotope dilution HRGC-HRMS method after a highly refined extraction on multi-layer column of silica gel and alumina layer and clean-up, and fractionations, followed by Hypercarb-HPLC and PYE-HPLC sub-fractionation steps. Contents of 117 chlorobiphenyls determined in pine needles varied for the 25 sites studied and is between 2.7 and 49 ng/g wet weight. The PCBs pollution and congener-specific composition of pine needles to some degree varied according to the site or region surveyed depending on population density and industrialization. Many of the country-side areas showed lower concentrations between 2.7 and 8.9 ng/g ww. Pine needles in areas close to well populated and industrial regions of Opole, Kutno, Wloclawek and Debica showed the highest PCB pollution with concentrations varying between 30 and 49 ng/g ww. The Kutno site showed the highest pollution and this fact probably can be explained by possible emission from transformer manufactures located at some distance west of the Kutno area. Factor analysis (FA) and depending on the site revealed on relationship of PCBs composition of pine needles both with highly chlorinated PCB constituents of the mixtures such as Chlorofen, Aroclor 1254, Aroclor 1268 and Sovol but also of lower chlorinated PCB constituents of Aroclor 1242, Aroclor 1248, Clophen A40 or Delor 103. Thermal processes were considered a less significant source of PCBs in ambient air over Poland compared to evaporative sources related to technical PCB formulations. Supplemental materials are available for this article. Go to the publisher's online edition of Journal of Environmental Science and Health: Part A to view the free supplemental file.

Dioxin-like compound compositional profiles of furnace bottom ashes from household combustion in Poland and their possible associations with contamination status of agricultural soil and pine needles.

A compositional profile of PCDDs, PCDFs, non- and mono-ortho PCBs, and PCNs of several type furnace bottom ashes obtained after the heating muffle stove for domestic use combustion of hard coal, coke, wood, and solid domestic waste mixture have been examined as possible contributors to environmental diffusion with these compounds in Poland. The uppermost concentration of dioxin-like compounds with 2.0 ng TEQ kg(-1) dry weight found for wood ash was dominated by PCDDs and PCDFs, while for other types of ashes were in the range from 0.052 ng TEQ kg(-1) to 0.67 ng TEQ kg(-1) dry weight. The multivariate statistical analysis displayed some compositional similarity of PCDDs, PCDFs and PCNs between the ashes and environmental pine needle or agricultural soil matrices collected in Poland.

Airborne chloronaphthalenes in Scots pine needles of Poland.

The amounts, profiles and origin of CNs (from triCNs to octaCN) sequestered in Scots pine needles collected from 25 spatially distant sites in Poland have been studied based on congener-specific data obtained after a several clean-up and fractionation steps and final HRGC/HRMS separation and determination. The absolute concentrations of CNs varied largely from site to site, i.e., by 15-fold. The sum of tri- to octaCN concentration at fifteen of the least contaminated sites ranged from 70 to 280 pg g(-1) ww, and at further eight sites were from 340 to 540 pg g(-1) ww, while at two the most contaminated were 1000 and 1100 pg g(-1)ww. There were some substantial similarities but also variations in triCN to octaCN homologue group profiles depending on the site. Among triCNs the isomers such as 1,2,4-/1,3,7-/1,4,6-triCNs (nos. 14/21/24) dominate in Scots pine needles. For majority of the sites examined 1,2,4-/1,3,7-/1,4,6-triCNs are also the major contributors to the bulk of CNs determined. Among tetraCNs isomer 1,2,5,8-tetraCN (no. 38) was dominant contributor at eighteen sites, while 1,2,4,6-/1,2,4,7-/1,2,5,7-tetraCN (nos. 33/34/37) at seven other sites. In the case of pentaCNs isomer 1,2,4,5,8-pentaCN (no. 59), was dominant contributor alone. Octachloronaphthalene frequently contributed substantially to the bulk of CNs. The Cluster Analysis and Principal Component Analysis did indicate that the compositional profiles of CNs found in Scots pine needles resemble somehow these found in the bottom ashes after coke and coal burning as well as of Halowax 1000 and 1099 formulations.

Polychlorinated dibenzo-p-dioxins (PCDDs) and -furans (PCDFs) in pine needles of Poland.

There is scarcity of data on sources, environmental diffusion and concentrations of PCDD/Fs and dioxin-like compounds in the Eastern and Central Europe. A study has been conducted using pine needles as passive matrix on diffusion of airborne 17 highly toxic PCDD/Fs in Poland. The target compounds were quantified using isotope dilution and HRGC/HRMS. One-year-old pine needles collected from 25 spatially distant sites in October 2002 revealed a relatively very low aerial emission and degree of pollution with PCDD/Fs. The most toxic 2,3,7,8-TCDD was absent (< 0.44 pg/g) in fresh pine needles sampled and absent at all sites were also 1,2,3,7,8-PeCDD, 1,2,3,4,7,8-HxCDD, 1,2,3,6,7,8-HxCDD, 1,2,3,7,8,9-HxCDD and 1,2,3,7,8,9-HxCDF (< 0.27 pg/g). OCDD at concentration range from 1.4 to 34 pg/g and OCDF at range from 1.5 to 41 pg/g were the only among 17 compounds found at each site, and next in prevalence was 1,2,3,4,7,8,9-HpCDF (total range from < 0.41 to 8.1 pg/g), which was found at 24 off 25 sites. The I-TEQ transformed concentrations of PCDD/Fs of pine needles of Poland ranged from < 0.01 to 1.28 pg/g ww or from 0.01 to 3.18 pg/g dw. The CDD/F homologue groups and congeners profiles of pine needles with highly dominant HpCDD/F and OCDD/F found in this survey suggest on lack of significant other than coal/lignite/wood combustiont sources of PCDD/Fs diffusion to ambient air in Poland.

Polychlorinated biphenyls and -naphthalenes in pine needles and soil from Poland--concentrations and patterns in view of long-term environmental monitoring.

Pine needles were selected as cost effective and easy collectable matrices suitable for long-term monitoring of the lower troposphere pollution with polychlorinated biphenyls and polychlorinated naphthalenes. The fingerprints of PCNs and PCBs in the top layers of agricultural soils were used for determination of point sources of pollution for terrestrial ecosystems. The new idea based on the use of nona- and decachlorinated isomers fingerprint as an additional tool suitable for the identification of potential point sources of pollution with PCBs, seemed to be a capable tool to identify contamination of soil and ambient air related to former manufacturing and the use of highly chlorinated technical PCB preparations.

Source determination of highly chlorinated biphenyl isomers in pine needles - comparison to several PCB preparations.

The isomer specific composition of 13 technical PCB formulations of different origin and of pine needles was analyzed using GC/MS and HRGC/HRMS. Nonachlorinated biphenyls were identified in 11 among 13 formulations analyzed, with the highest abundance found for highly chlorinated ones (Aroclors 1268 and 1260, Chlorofen, Sovol, Kanechlors 600 and 500, Delor 106, Clophen A60). Decachlorobiphenyl was identified only in Aroclor 1268, Clophen A60, Aroclor 1260 and Chlorofen, comprising, respectively, 8.9, 2.8, 1.3 and 0.82% of the total bulk of nona- and decaCBs detected. Nona- and decaCB were detected in pine needles in Poland with the highest concentrations found at the sites neighboring to a former production sites of the Polish PCB formulations, while in pine needles collected around the Tokyo Bay nona- and decacCB were detected only in four of 10 sites and the concentrations corresponded to those found at the rural areas of Poland.

Dioxin-like compounds in pine needles around Tokyo Bay, Japan in 1999.

Pine needle samples collected at ten spatially distant sites around Tokyo Bay in 1999 indicated a widespread lower troposphere pollution with ultra-trace dioxin-like compounds such as chlorodibenzo-p-dioxins (PCDDs), -furans (PCDFs), non-ortho- and mono-ortho-chlorobiphenyls (pPCBs), and -naphthalenes (PCNs). Elevated concentration of planar PCBs and the total PCNs were found at the sites which are located innermost to the Bay, suggesting the regional importance of the evaporative nature of the source of pollution by those compounds over this vast area. The concentrations and profiles for PCDDs and PCDFs remained largely uniform. An exception was the site near the town of Tateyama in the Chiba Prefecture, which is the southernmost but also relatively separate from the inner Bay. The site near Tateyama showed somehow background contamination with all compound groups and highly different profiles of PCNs. The principal component analysis (PCA) of the data matrix has revealed that around the Tokyo Bay, apart from the evaporative emission sources for PCNs and PCBs, combustion related processes also play an important role as sources of the ambient air contamination not only with PCDDs/Fs but also with chloronaphthalenes and planar chlorobiphenyls.