Trends in background levels of persistent organic pollutants at Kosetice observatory, Czech Republic.1) Part I. Ambient air and wet deposition 1996-2005

Kosetice observatory is a facility of the Czech Hydrometeorological Institute, which is a part of the European Monitoring and Evaluation Programme (EMEP) network. Persistent organic pollutants (POPs: PCBs, DDTs, HCHs, PAHs) have been monitored in all environmental matrices using the integrated monitoring approach. Generally, the atmospheric levels of POPs in this Central European background station (mean values: 0.115 ng m(-3) for SigmaPCBs, 0.040 ng m(-3) for SigmaDDTs, 0.077 ng m(-3) for SigmaHCHs, and 17 ng m(-3) for SigmaPAHs) are significantly higher than those in other EMEP stations localized mostly in Northern and Western Europe. Long-term trends of POP concentrations in the ambient air and wet deposition are presented in this article and they show a slow decline in the last decade for most of the investigated compounds. Temporally increased levels of certain chemicals were associated with some local climatic (floods) or socio-economic (fuel prices) factors.     

An assessment of persistent organic pollutants in Scottish coastal and offshore marine environments

Concentrations of persistent organic pollutants (POPs), including polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) were determined in sediment and biota (fish liver) from around Scotland. The concentrations were investigated using assessment criteria developed by OSPAR and ICES. Organic contaminant concentrations, PAHs, PCBs and PBDEs in sediment, and PCBs and PBDEs in fish liver, were significantly higher in the Clyde compared to all other sea areas. This is mainly due to historic industrial inputs. Highest PCB and PAH concentrations were found in the strata furthest up the Clyde estuary, with concentrations of POPs in these strata being at levels such that there is an unacceptable risk of chronic effects occurring in marine species. Furthermore, for PAHs in Clyde sediment there was a significant negative gradient going from north to south towards the open sea. PAH and PCB concentrations in sediment and biota in all other Scottish sea areas (except for PCBs in sediment from East Scotland) were unlikely to give rise to pollution effects, being below relevant assessment criteria. Although no assessment criteria are available for PBDEs, the concentrations observed in Scottish sediments were low with all congeners below the limit of detection (LoD; 0.03 μg kg(-1) dry weight) in 140 out of a total of 307 samples analysed. Where PBDEs were detected, the dominant congeners were BDE47 and BDE99. PBDEs were detected in fish livers, although concentrations were less than 150 μg kg(-1) lipid weight in all sea areas except the Clyde where concentrations ranged between 8.9 and 2202 μg kg(-1) lipid weight. Few trends were detected in contaminant concentrations in biota or sediment at any Scottish site with more than five years data. Downward trends were detected in PAHs in sediment from the Clyde, Irish Sea and Minches and Malin Sea and PCBs in fish liver from the Moray Firth. Rules were developed for the aggregation of the contaminant data across a sea area. An overall assessment for each sea area was then assigned, looking at the frequency of sites or strata within each sea area that were above or below the relevant assessment criteria. Overall the status of the various sea areas, with respect to the assessed POPs, can be considered to be acceptable in that they were below concentrations likely to result in chronic effects for all sea areas except the Clyde.     

Detecting and characterising sources of persistent organic pollutants (PAHs and PCBs) in surface sediments of an industrialized area (harbour of Trieste, northern Adriatic Sea)

A sediment sampling based on a two-dimensional mapping was performed in the harbour of Trieste (northern Adriatic Sea), considering 28 sites exposed to pollutant inputs from harbour and industrial activities. Polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) were determined in surface sediments, because these very persistent pollutants seem to be responsible for the depletion of benthic populations observed in this area. The correlation matrix indicates that PAHs and PCBs are non-correlated, and probably have different sources. Both cluster analysis performed on the sampling sites and graphical drawing of the PAH sediment contents make it possible to locate along the shoreline a band of more polluted sediments, clustered around a site facing a steelmaking factory, to be considered as the main source point for PAHs. The evaluation of phenanthrene to anthracene (P/AN) and fluoranthene to pyrene (FL/PY) ratios permits the assessment of the pyrolytic, industrial origin of these PAHs, rejecting a second possible source of hydrocarbons (i.e., an oil-pipeline terminal, situated near the steelmaking factory). Graphical drawing of the total PCB iso-concentrations reveals a different source-point for this other category of very persistent pollutants.     

A long-term survey of heavy metals and specific organic compounds in biofilms, sediments, and surface water in a heavily affected river in the Czech Republic

To assess the long-term anthropogenic load of the Bílina River (Czech Republic), the concentrations of heavy metals and specific organic compounds in different river ecosystem matrices (water, biofilms, and sediments) were determined. Although the current concentrations of pollutants in surface water are low, frequently below the limits of the quantitative analytical methods used, the river ecosystem is still heavily loaded by anthropogenic pollution, mainly from the chemical and mining industries. This was demonstrated by analyzing biofilms and sediments. These matrices are more accurate representatives of the actual situation in the river and do not depend on hydrological conditions or random variability in water quality. The results indicate that the middle and the lower parts of the river are heavily polluted by mercury, arsenic, vanadium, polychlorinated biphenyls, hexachlorobenzene, and dichloro-diphenyl-trichloroethane. As a tributary of the Elbe River, the Bílina River represents a significant risk for the development of quality in this major European river.     

Organic pollutants in compost and digestate. Part 2. Polychlorinated dibenzo-p-dioxins, and -furans, dioxin-like polychlorinated biphenyls, brominated flame retardants, perfluorinated alkyl substances, pesticides, and other compounds

Compost and digestate are important recycling fertilizers and have beneficial effects on soil parameters. However, they can contain significant amounts of organic pollutants. Here, the first comprehensive data set on dibenzo-p-dioxins and -furans (PCDD/F), dioxin-like polychlorinated biphenyls (DL-PCB), brominated flame retardants, perfluorinated alkyl substances (PFAS), pesticides, phthalates, nonylphenol and chlorinated paraffins (CP) in source-separated compost and digestate from Switzerland is presented (n = 3-18). The median summation 17PCDD/F and summation 12DL-PCB concentrations were at 3.2 ng I-TEQ kg(-1)dry weight (dw) and 3.0 ng WHO-TEQ kg(-1)dw, respectively. Brominated diphenyl ether 209 (BDE 209) accounted for 72% of the total polyBDE content (10 microg kg(-1)dw). Hexabromocyclododecane (HBCD) and tetrabromobisphenol A (TBBPA) levels were at 100 and 0.51 microg kg(-1)dw, respectively. PFAS were identified for the first time in compost and digestate (median concentration 6.3 microg kg(-1)dw, summation 21compounds). Out of 269 pesticides analysed, 30 fungicides, 14 herbicides, eight insecticides and one acaricide were detected. Di-(2-ethylhexyl)phthalate (DEHP) median concentration accounted for 280 microg kg(-1)dw and nonylphenol was below the detection limit of 1 mg kg(-1)dw. The sum of short and medium chain CP was between 90 and 390 microg kg(-1)dw. The concentrations observed were at or above the levels found in background soils, which are the main recipient of compost and digestate. Where actually applied, compost can contribute considerably to the total input of organic pollutants to the soil. However, on a total Swiss agricultural area base, inputs seem to be limited.     

Enrichment of organic pollutants in the sea surface microlayer (SML) at Terra Nova Bay, Antarctica: influence of SML on superficial snow composition

Concentrations of dissolved and particle-associated n-alkanes, phthalates and polycyclic aromatic hydrocarbons (PAHs) were measured in sea surface microlayer (SML) and sub-surface water (SSL) samples collected in the coastal area of Terra Nova Bay, Antarctica, during the Austral spring 1998/1999. SML concentrations of the selected organic compounds were higher than SSL values and the enrichment factors were greater in the particulate phase than in the dissolved phase. During the same campaign, "fresh" snow samples, collected at different altitudes (from sea level up to 2670 m) near the coast on Mt Melbourne, immediately after a snowy event, were analysed in order to provide more information on air/sea exchange processes. The same classes of organic compounds found in sea water were also present in "fresh" snow samples. The surfactant fluorescent organic matter (SFOM), adsorbed on the microdrop aerosol surface, could be considered the main constituent of the enrichment and the carrier at higher altitudes of organic compounds. In fact, hydrocarbons (n-alkanes and PAHs), which are not surfactants like phthalates, could interact with SFOM and follow the same fate.     

Chemical trends in background air quality and the ionic composition of precipitation for the period 1980-2004 from samples collected at Valentia Observatory, Co. Kerry, Ireland

A major Irish study, based upon more than 8000 samples collected over the measurement period of 22 years, for sulfur dioxide (SO2-S), sulfate (SO4-S) and nitrogen dioxide (NO2-N) concentrations (microg m(-3)) within air, and the ionic composition of precipitation samples based on sodium (Na+), potassium (K+), magnesium (Mg2+), calcium (Ca2+), chloride (Cl-), sulfate (SO4-S), non-sea salt sulfate (nssSO4-S), ammonium (NH4-N), and nitrate (NO3-N) weighted mean concentrations (mg l(-1)), has been completed. For the air samples, the sulfur dioxide and sulfate concentrations decreased over the sampling period (1980-2004) by 75% and 45%, respectively, whereas no significant trend was observed for nitrogen dioxide. The highest concentrations for sulfur dioxide, sulfate and nitrogen dioxide were associated with wind originating from the easterly and northeasterly directions i.e. those influenced by Irish and European sources. The lowest concentrations were associated with the westerly directions i.e. for air masses originating in the North Atlantic region. This was further verified with the use of backward (back) trajectory analysis, which allowed tracing the movement of air parcels using the European Centre for Medium range Weather Forecasting (ECMWF) ERA-40 re-analysis data. High non-sea salt sulfate levels were being associated with air masses originating from Europe (easterlies) with lower levels from the Atlantic (westerlies). With the precipitation data, analysis of the non-sea salt sulfate concentrations showed a decrease by 47% since the measurements commenced.     

Long-term relationships between SO2 and NOx emissions and SO4(2-) and NO3- concentration in bulk deposition at the Hubbard Brook Experimental Forest, NH

A highly significant second-order polynomial relation between SO(2) emissions and SO(4)(2-) concentrations during 1970-2000 (r(2)= 0.80, p= <0.001), and a linear relation between NO(x) and NO(3)(-) concentrations during 1991-2000 (r(2)= 0.67, p= 0.004) in bulk precipitation were found for the Hubbard Brook Experimental Forest, NH based on emissions from a 24 h, back-trajectory determined source area. Earlier periods (1965-1980) for SO(2)ratio SO(4)(2-) and longer periods (1965-2000) for NO(x)ratio NO(3)(-) had poorer linear relations, r(2)= 0.03, p= 0.51 and r(2)= 0.22, p= 0.004, respectively. Methodology by the US Environmental Protection Agency for calculating emissions data during this period has changed significantly and frequently, making trend analysis difficult. Given the large potential for errors in estimating emissions and to a lesser extent, deposition, the robust relations between SO(2) emissions and SO(4)(2-) concentrations in bulk precipitation at the Hubbard Brook Experimental Forest show that careful, long-term measurements from a single monitoring site can provide sound and reasonable data on trends in air pollution.     

Study on determination of iron,cobalt, nickel,copper, zinc and manganese in drinking water by solid-phase extraction and RP-HPLC with 2-(2-quinolinylazo)-5-diethylaminophenol as precolumn derivatizing reagent

A new method for the determination of iron, cobalt, nickel, copper, zinc and manganese in drinking water by the reversed-phase high-performance liquid chromatography (RP-HPLC) with 2-(2-quinolinylazo)-5-diethylaminophenol (QADEAP) as precolumn derivatizing reagent was studied in this paper. The iron, cobalt, nickel, copper, zinc, and manganese ions react with QADEAP to form color chelates in the presence of cetyl trimethylammonium bromide (CTMAB) and acetic acid-sodium acetic buffer solution medium of pH 4.0. These chelates were enriched by solid-phase extraction with a Waters Nova-Pak C18 cartridge and eluted the retained chelates from the cartridge with tetrahydrofuran (THF). The enrichment factor of 100 was achieved. Then the chelates were separated on a Waters Nova-Pak C18 column (3.9 x 150 mm, 5 microm) by gradient elution with methanol (containing 0.2% of acetic acid and 0.1% of CTMAB) and 0.05 mol L(-1) acetic acid-sodium acetic buffer solution (containing 0.1% of CTMAB) (pH 4.0) as mobile phase at a flow rate of 0.5 ml min(-1), and monitored with a photodiode array detector from 450 approximately 700 nm. The detection limits (S/N = 3) of iron, cobalt, nickel, copper, zinc and manganese are 0.8, 1.1, 0.9, 1.1, 1.5 and 2.0 ng L(-1), respectively, in the original sample. This method can be applied to determination at the microg L(-1) level of iron, cobalt, nickel, copper, zinc and manganese in drinking water with good results.     

Heavy metal and selenium levels in feathers of herring gulls (Larus argentatus): Differences due to year,gender, and age at Captree,Long Island

The concentrations of heavy metals (mercury, lead, cadmium, chromium, manganese) and selenium in the feathers of herring gulls (Larus argentatus) from a nesting colony at Captree, Long Island, New York were examined from 1989 to 1993 to determine if there were differences from year to year, and between males and females, adult and young, and dead versus live gulls. Variation in metal levels in regression models was explained by age (all metals), year (all except manganese), and whether the feathers were from live or dead birds (all except lead and chromium). The feathers of adults had significantly higher levels of mercury, lead and manganese than those of young, but lower levels of selenium and cadmium than those of young. Levels in down and fledgling feathers were similar for lead, cadmium and selenium, but fledgling feathers had higher levels for mercury, chromium, and manganese. There were no gender differences in metal levels for adult feathers except for lead (females had higher levels). Levels of mercury and manganese were higher in feathers of live adults whereas levels of cadmium and selenium were higher in the feathers of dead adults.     

The determination of cobalt(II) at DME using catalytic hydrogen current technique in various water samples, agricultural materials and pharmaceuticals

Two novel and facile ligands ammonium piperidine dithiocarbamate (Amm Pip-DTC) and ammonium morpholine dithiocarbamate (Amm Mor-DTC) were synthesized for the development of rapid and cost effective catalytic hydrogen current technique to analyze cobalt(II) in the presence of NH(4)Cl-NH(4)OH at pH 7.8 and 8.4 with Amm Pip-DTC and Amm Mor-DTC. These ligands produce catalytic hydrogen currents with Co(II) at peak potentials -1.24 V and -1.44 V vs. SCE respectively. Quantitative experimental conditions are developed by studying effect of pH, supporting electrolyte (NH(4)Cl), ligand and metal ion concentrations and effect of adverse ions on peak height to improve the sensitivity, selectivity and detection limits of the catalytic hydrogen current technique and compared it in terms of Student's t test and variance ratio f test with differential pulse polarographic (DPP) method. The developed technique was applied for the analysis of cobalt(II) in various water samples, agricultural materials and pharmaceuticals and the results obtained are in good agreement with the DPP data.     

Assessment and Treatment of Hydrocarbon Inundated Soils Using Inorganic Nutrient (N-P-K) Supplements: II. A Case Study of Eneka Oil Spillage in Niger Delta, Nigeria

Polluted soils from Eneka oil field in the Niger delta region of Nigeria were collected two months after recorded incidence of oil spillage as part of a two-site reclamation programme. The soils were taken on the second day of reconnaissance from three replicate quadrats, at surface (0–15 cm) and subsurface (15–30 cm) depths, using the grid sampling technique. Total extractable hydrocarbon content (THC) of the polluted soils ranged from 1.006×10³–5.540× 10⁴ mg/kg at surface and subsurface depths (no overlap in Standard Errors at 95% Confidence Level). Greenhouse trials for possible reclamation were later carried out using (NH₄)₂SO₄, KH₂PO₄ and KCl (N-P-K) fertilizer as nutrient supplements. Nitrogen as NO₃-N and potassium were optimally enhanced at 2% (w/w) and 3% (w/w) of the N-P-K supplementation respectively. Phosphorus, which was inherently more enhanced in the soils than the other nutrients, maintained same level impact after 20 g treatment with the N-P-K fertilizer. Total organic carbon (%TOC), total organic matter (%TOM), pH and % moisture content all provided evidence of enhanced mineralization in the fertilizer treated soils. If reclamation of the crude oil inundated soils is construed as the return to normal levels of metabolic activities of the soils, then the application of the inorganic fertilizers at such prescribed levels would duly accelerate the remediation process. This would be, however, limited to levels of pollution empirically defined by such THC values obtained in this study. The data on the molecular compositional changes of the total petroleum hydrocarbon content (TPH) of the spilled-oil showed the depletion of the fingerprints of the n-paraffins, nC₈–nC₁₀, and complete disappearance of C₁₂–C₁₇ as well as the acyclic isoprenoid, pristane, all of which provided substantial evidence of degradation.