Serum concentrations of chlorinated dibenzo-p-dioxins and dibenzofurans among former New Zealand trichlorophenol workers

This study examined serum levels of 2,3,7,8-substituted chlorinated dioxins and furans, and 15 PCBs for 346 New Zealand employees who worked at a site that manufactured 2,4,5-trichlorophenol (TCP) and 2,4,5-trichlorophenoxy acetic acid (2,4,5-T). Participants with potential TCP or 2,4,5-T exposures had mean lipid-adjusted 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) levels of 9.9 ng kg⁻¹ lipid compared to 4.9 ng kg⁻¹ for workers with no exposure at the site. Among exposed workers, we found evidence of differences in 2,3,7,8-TCDD levels by department and duties. Workers involved in an accidental release had the highest mean 2,3,7,8-TCDD levels, 37.9 ng kg⁻¹, followed by workers in the trichlorophenol plant, 23.4 ng kg⁻¹. Workers with potential intermittent exposures to 2,3,7,8-TCDD in construction, maintenance, mechanics, and transport had 2,3,7,8-TCDD levels above New Zealand background levels of 3.9 ng kg⁻¹, indicating workplace exposures. Among participants with work history indicating no 2,3,7,8-TCDD exposures, we observed some individuals with 2,3,7,8-TCDD levels above background levels. However, in most cases, these workers reported workplace exposures not recorded on their work histories or held other jobs with the potential for 2,3,7,8-TCDD exposures outside the plant. All other dioxin, furan, and PCB levels were similar among the exposed and unexposed workers.     

Influence of tidal regime on the distribution of trace metals in a contaminated tidal freshwater marsh soil colonized with common reed (Phragmites australis)

A historical input of trace metals into tidal marshes fringing the river Scheldt may be a cause for concern. Nevertheless, the specific physicochemical form, rather than the total concentration, determines the ecotoxicological risk of metals in the soil. In this study the effect of tidal regime on the distribution of trace metals in different compartments of the soil was investigated. As, Cd, Cu and Zn concentrations in sediment, pore water and in roots were determined along a depth profile. Total sediment metal concentrations were similar at different sites, reflecting pollution history. Pore water metal concentrations were generally higher under less flooded conditions (mean is (2.32 ± 0.08) × 10⁻³ mg Cd L⁻¹ and (1.53 ± 0.03) × 10⁻³ mg Cd L⁻¹). Metal concentrations associated with roots (mean is 202.47 ± 2.83 mg Cd kg⁻¹ and 69.39 ± 0.99 mg Cd kg⁻¹) were up to 10 times higher than sediment (mean is 20.48 ± 0.19 mg Cd kg⁻¹ and 20.42 ± 0.21 mg Cd kg⁻¹) metal concentrations and higher under dryer conditions. Despite high metal concentrations associated with roots, the major part of the metals in the marsh soil is still associated with the sediment as the overall biomass of roots is small compared to the sediment.     

Altitude dependence of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in surface soil from Tibetan Plateau, China

Remote mountain areas besides high latitude regions are beginning to receive increased attention in studying the transport and behavior of persistent organic pollutants (POPs). In the present work, surface soil samples were collected from the Tibetan Plateau, the highest plateau in the world which includes the northern slope of Mt. Qomolangma, to investigate the levels and trends of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) along the altitudinal gradient. The average PCB and PBDE concentrations were 185.6 ng kg⁻¹ dry weight (dw) (range 47.1–422.6 ng kg⁻¹ dw) and 11.1 ng kg⁻¹ dw (range 4.3–34.9 ng kg⁻¹ dw), respectively. Regression analysis between the log-transformed TOC-normalized concentrations and the altitudes of the sampling sites showed two opposite trends with regard to altitude dependence: negative relationship with altitude below about 4500 m followed by a positive altitude dependence above this point. Considering minimum anthropogenic activities and very sparse precipitation in the north of Himalayas, the trends above 4500 m imply that the significant altitude dependence of these two groups of POPs were irrespective of pollution sources, but could be predicted by the global distillation effect involving cold condensation in high altitude mountain areas. Increasing levels of heavier congeners were found in higher altitude sites, although the lighter congeners were the main contributors to the total amount, suggesting that less volatile congeners seem to become enriched easier than those more volatile at higher altitudes in this region.     

Bioaccumulation of polybrominated diphenyl ethers in harbor seals from the northwest Atlantic

Polybrominated diphenyl ethers (PBDEs) were analyzed in blubber of harbor seals (Phoca vitulina concolor) collected between 1991 and 2005 along the northwest Atlantic. ∑PBDE concentrations (mono- to hexa-BDEs) detected in blubber samples (n = 42) ranged from 80 to 25 720 ng g⁻¹ lw, (overall mean 2403 ± 5406 ng g⁻¹ lw). By age, mean ∑PBDE concentrations were: 3645 ± 7388, 2945 ± 5995, 1385 ± 1265, and 326 ± 193 ng g⁻¹ lw in pups, yearlings, adult males, and adult females, respectively. Unlike the trend for PCBs, no decreasing gradient from urban to rural/remote areas was observed for PBDEs in these samples, likely reflecting inputs from local sources. No significant temporal trend was observed for PBDEs in harbor seals between 1991 and 2005, although congener profiles shifted over time. Tetra-BDE-47 was the dominant congener, followed by BDEs-99, -100, -153, -154, and -155 in varying order, suggesting exposure to the penta-BDE product. In adult males, the hexa-BDEs contributed more to the total (22%) than BDEs-99 and -100 (14%), and concentrations of BDE-155 were elevated compared with -154. Higher BDEs were detected in a subset of seals (n = 12) including hepta-BDE-183, the marker for the octa-BDE mixture, and octa-BDE-197, along with several unidentified hepta- and octa- congeners. BDE-209 was detected in seal blubber at concentrations ranging from 1.1 to 8 ng g⁻¹ lw, indicating that deca-BDE is bioavailable in this marine food web. This is the first study to document the accumulation of BDE-209 at measurable levels in wild harbor seals. While the PBDE patterns in blubber indicate exposure to all three BDE commercial mixtures, the data also suggest that BDE-209 debromination by seal prey fish may contribute to the loading of lower brominated congeners (hexa- to octa-BDEs) in these seals.     

Organochlorine pesticides in surface sediments and suspended particulate matters from the Yangtze estuary, China

Total HCHs' and total DDTs' levels in surface sediments (SS) ranged from 0.5 to 17.5 ng g⁻¹ and from 0.9 to 33.1 ng g⁻¹, averaged 6.0 and 8.2 ng g⁻¹, respectively. Total HCHs' and total DDTs' levels in suspended particulate matters (SPM) varied from 6.2 to 14.8 ng g⁻¹ with a mean value of 12.3 ng g⁻¹ and were from 3.4 to 25.7 ng g⁻¹ with an average of 16.4 ng g⁻¹, respectively. Lindane is the main HCHs' source and continuing use in the Yangtze Delta areas of ‘pure’ γ-HCH (lindane) rather than technical HCH (a mix of largely α- and some γ-HCH). DDTs in SS are mainly accumulated in history. However, high DDT fractions in SPM are indicators of new input of typical dicofol type DDT from 2002 to 2004. It can be seen that most samples from the Yangtze estuary were in ranges where adverse biological effects are expected, either occasionally or frequently.     

Vertical distribution of polycyclic aromatic hydrocarbons in atmospheric boundary layer of Beijing in winter

Air samples were collected using active samplers at various heights of 8, 15, 32, 47, 65, 80, 102, 120, 140, 160, 180, 200, 240, 280 and 320 m on a meteorological tower in an urban area of Beijing in two campaigns in winter 2006. Altitudinal distributions of polycyclic aromatic hydrocarbons (PAHs) in atmospheric boundary layer of Beijing in winter season were investigated. Meteorological conditions during the studied period were characterized by online measurements of four meteorological parameters as well as trajectory calculation. The mean total concentrations of 15 PAHs except naphthalene of gaseous and particulate phase were 667±450 and 331±144 ng m⁻³ in January and 61±19 and 29±6 ng m⁻³ in March, respectively. Domestic coal combustion and vehicle emission were the dominant PAH sources in winter. Although the composition profiles derived from the two campaigns were similar, the concentrations were different by one order of magnitude. The higher concentrations in January were partly caused by higher emission due to colder weather than March. Moreover, weak wind, passing through the city center before the sampling site, picked up more contaminants on the way and provided unfavorable dispersion condition in January. For both campaigns, PAH concentrations decreased with heights because of ground-level emission and unfavorable dispersion conditions in winter. The concentration ratio of PAHs in gas versus solid phases was temperature dependent and negatively correlated to their octanol–air partition coefficients.     

Adsorption of uranium(VI) on amorphous ferric oxyhydroxide at high concentrations of dissolved carbon(IV) and sulfur(VI)

Amorphous ferric oxyhydroxide is being used to treat groundwater contaminated with uranium(VI); the compound also has potential for use as a component in in situ chemical barriers. To quantitatively evaluate its effectiveness in such applications, adsorption of uranium(VI) onto amorphous ferric oxyhydroxide was experimentally investigated under a wide range of uranium(VI) (8.40·10⁻⁷−2.10·10⁻³ mol L⁻¹; 0.2–500 mg L⁻¹), sulfur(VI) (0–0.07 mol L⁻¹; 0–2240 mg L⁻¹) and carbon(IV) (0–0.0195 mol L⁻¹; 0–234 mg L⁻¹) concentrations, and pH-values (4–9.6). The adsorption behavior of uranium(VI) (uranyl ion and its complexes) is similar to that of other cations; it exhibits a sharp rise in the extent of adsorption with increasing pH. Interactions among uranyl complexes and surface sites are interpreted using a site complexation model. Although the model does not incorporate electrostatics and includes only a single type of adsorption site, it provides a reasonable match to measured adsorption and proton exchange data. The simplicity of the model and the resulting reduction in computational demand allow its efficient incorporation into coupled reaction-transport models.     

A new direct thermal desorption-GC/MS method: Organic speciation of ambient particulate matter collected in Golden, BC

Particulate matter having an aerodynamic diameter less than 2.5 μm (PM2.5) is thought to be implicated in a number of medical conditions, including cancer, rheumatoid arthritis, heart attack, and aging. However, very little chemical speciation data is available for the organic fraction of ambient aerosols. A new direct thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS) method was developed for the analysis of the organic fraction of PM2.5. Samples were collected in Golden, British Columbia, over a 15-month period. n-Alkanes constituted 33–98% by mass of the organic compounds identified. PAHs accounted for 1–65% and biomarkers (hopanes and steranes) 1–8% of the organic mass. Annual mean concentrations were: n-alkanes (0.07–1.55 ng m⁻³), 16 PAHs (0.02–1.83 ng m⁻³), and biomarkers (0.02–0.18 ng m⁻³). Daily levels of these organics were 4.89–74.38 ng m⁻³, 0.27–100.24 ng m⁻³, 0.14–4.39 ng m⁻³, respectively. Ratios of organic carbon to elemental carbon (OC/EC) and trends over time were similar to those observed for PM2.5. There was no clear seasonal variation in the distribution of petroleum biomarkers, but elevated levels of other organic species were observed during the winter. Strong correlations between PAHs and EC, and between petroleum biomarkers and EC, suggest a common emission source – most likely motor vehicles and space heating.     

Comportement photochimique du nitro-4 phenol en solution aqueuse

The quantum yield of the phototransformation of 4-nitrophenol has been evaluated as 4.5×10⁻⁵±0.6×10⁻⁵ at pH=2; at 3.0×10⁻⁵±0.6×10⁻⁵ at pH=5.5; 1.8×10⁻⁵±0.5×10⁻⁵ at pH=8.3. However the half-life is relatively low and no accumulation of aromatic or quinonic products was observed. Hydroquinone (QH₂) is the main organic primary product formed when an air-saturated or degassed solution was irradiated in 365 nm monochromatic light (about 80% of the 4-nitrophenol initially converted at pH=5.5 in the absence of oxygen). In air-saturated neutral or acidic solution, the formation of NO⁻₃ ions accounted for about 80% of the 4-nitrophenol converted, but in degassed medium a mixture NO : NO⁻₂ : NO⁻₃ is formed. An heterolytical mechanism of photohydrolysis with primary formation of QH₂ and HNO₂ is suggested. Several by-products as benzoquinone, 4-nitrosophenol, 4-nitrocatechol and nitrohydroquinone are formed according to the conditions. Many secondary reactions are involved as the disproportionation or the oxidation of HNO₂, the oxidation of QH₂ by HNO₂ and oxidations induced by excitation of NO⁻₂ and NO⁻₃.     

Do aerosols act as catalysts in the OH radical initiated atmospheric oxidation of volatile organic compounds?

Smog chamber/FTIR techniques were used to study the relative reactivity of OH radicals with methanol, ethanol, phenol, C₂H₄, C₂H₂, and p-xylene in 750 Torr of air diluent at 296±2 K. Experiments were performed with, and without, 500–8000 μg m⁻³ (4000–50 000 μm² cm⁻³ surface area per volume) of NaCl, (NH₄)₂SO₄ or NH₄NO₃ aerosol. In contrast to the recent findings of Oh and Andino (Atmospheric Environment 34 (2000) 2901, 36 (2002) 149; International Journal of Chemical Kinetics 33 (2001) 422) there was no discernable effect of aerosol on the rate of loss of the organic compounds via reaction with OH radicals. Gas kinetic theory arguments cast doubt upon the findings of Oh and Andino. The available data suggest that the answer to the title question is “No”. As part of this work the rate constants for reactions of OH radicals with methanol, ethanol, and phenol in 750 Torr of air at 296 K were determined to be: k_OH+CH3OH=(8.12±0.54)×10⁻¹³, k_OH+C2H5OH=(3.47±0.32)×10⁻¹² and k_OH+phenol=(3.27±0.31)×10⁻¹¹ cm³ molecule⁻¹ s⁻¹.     

Environmental release of dioxins from reservoir sources during beach nourishment programs

In late 1990s, USEPA/FDA made an important connection regarding the presence of elevated levels of dioxins (e.g., 1500 ng kg⁻¹ TEQ) in ball clays mined in Mississippi (USA) from a geological deposit dated to ∼40 million years (Mississippi Embayment) that stretches over several states (northern part of Mississippi to Kentucky) and levels of dioxins in selected animal food sources. Following a recent beach nourishment program along the mid-Atlantic coast of the US, a number of dark gray, blue tinted nuggets of varying sizes were found on beach strands and near the shoreline. Using the presence of these balls of clay (shape, color, and knowledge regarding their use in pottery) on the beach, together with our direct experience analyzing ball clays for dioxins, we made a possible association between these clays and elevated dioxins. Concerns regarding the potential of nourishment programs to cause severe damage to our beaches drove us to test the dioxin content of nourishment exposed clays. A number of the nuggets, along with freshly dredged and deposited sand (collected the morning after nourishment) with the same coloration, and others (sun-bleached), collected approximately 2 weeks after the completion of the nourishment efforts, were analyzed for the presence of PCDD/Fs, PCBs, and selected semi-volatile chlorinated organics. The clay PCDD/F WHO2005-TEQs (dry weight; ND = DL; EMPC = EMPC) ranged from 0.41 to 5.78 ng kg⁻¹ with an average of 2.64 ng kg⁻¹, whereas the sand sample’s TEQs ranged from 0.18 to 0.31 ng kg⁻¹ PCDD/F WHO-2005, with an average of 0.22 ng kg⁻¹. The average total tetra- through octachlorinated dibenzo-p-dioxin concentration was 2700 ng kg⁻¹ (with a maximum of 5800 ng kg⁻¹) for the clays and 8.5 ng kg⁻¹ (with a maximum of 16.8 ng kg⁻¹) for the sand samples. The congener 2,3,7,8-TCDD (TEF = 1) was detected in half of the clay samples (0.11-0.77 ng kg⁻¹). All of the clay and sand samples displayed an unambiguous and dominating 1,4,6,9-chlorination pattern across homolog groups. No other chlorinated aromatics were detected above background levels. The observations, along with the absence or an extremely low level of polychlorinated dibenzofurans, together with the mineralogical analysis, supports the conclusion that off-shore dredging activities are reaching reservoir sources containing dioxin-tainted, smectic/kaolinite clay minerals. Subsequent beach erosion provides additional environmental releases over time, as buried balls of clay from previous nourishment efforts become exposed.     

An aerosol flow tube study of the interaction of N2O5 with calcite, Arizona dust and quartz

The interaction of N₂O₅ with dispersed samples of Arizona Test Dust (ATD), Calcite (CaCO₃) and quartz (SiO₂) was investigated at varying relative humidity using an aerosol flow reactor. Reactive uptake coefficients, γ, obtained at close to zero relative humidity were (4.8 ± 0.7) × 10⁻³ for CaCO₃, (8.6 ± 0.6) × 10⁻³ for Quartz and (9.8 ± 1.0) × 10⁻³ for ATD. In the case of calcite, evidence was obtained for an enhanced rate of uptake at relative humidities above ≈ 50%. The results are compared to literature values obtained using bulk substrates and to previous aerosol uptake data on Saharan dust.     

Levels and composition of volatile organic compounds on commuting routes in Detroit, Michigan

Vehicle emissions can constitute a major share of ambient concentrations of many volatile organic compounds (VOCs) and other air pollutants in urban areas. Especially high concentrations may occur at curbsides, vehicle cabins, and other microenvironments. Such levels are not reflected by monitoring at fixed sites. This study reports on measurements of VOCs made from buses and cars in Detroit, MI. A total of 74 adsorbent tube samples were collected on 40 trips and analyzed by GC-MS for 77 target compounds. Three bus routes, selected to include residential, commercial and heavily industrialized areas, were sampled simultaneously on four sequential weeks during morning and afternoon rush hour periods. Nineteen compounds were regularly detected and quantified, the most prevalent of which included hexane/2-methyl pentane (15.6±5.8 μg m⁻³), toluene (10.2±7.9 μg m⁻³), m,p-xylene (6.8±4.7 μg m⁻³), benzene (4.5±3.0 μg m⁻³), 1,2,4-trimethylbenzene (4.0±2.6 μg m⁻³), o-xylene (2.2±1.6 μg m⁻³), and ethylbenzene (2.1±1.5 μg m⁻³). VOC levels in bus interiors and outdoor levels along the roadway were similar. Despite the presence of large industrial sources, route-to-route variation was small, but temporal variation was large and statistically significant. VOC compositions and trends indicate the dominance of vehicle sources over the many industrial sources in Detroit with the possible exceptions of styrene and several chlorinated VOCs. In-bus levels exceeded concentrations at fixed site monitors by a factor of 2–4. VOC concentrations in Detroit traffic are generally comparable to levels measured elsewhere in the US and Canada, but considerably lower than measured in Asia and Europe.     

A study of the atmospheric reaction of CH3S with O3 as a function of temperature

The atmospheric reaction of the methylthiyl radical (CH₃S) with O₃ was investigated as a function of temperature (259–381 K), in the pressure range of 25–300 Torr, using the technique of laser photolysis/laser-induced fluorescence. The resulting Arrhenius expression, with an uncertainty of ±2σ, was k₁(T=259–381 K)=(1.02±0.30)×10⁻¹² exp[(432±77) K/T] cm³ molecule⁻¹ s⁻¹. The obtained rate constant k₁ was independent of pressure over the limited range employed. Our results are compared with the previous studies carried out, at single temperature and as a function of temperature, by different techniques.     

Kinetics of OH-initiated oxidation of oxygenated organic compounds in the aqueous phase: new rate constants, structure–activity relationships and atmospheric implications

The kinetics of OH oxidation of several organic compounds of atmospheric relevance were measured in the aqueous phase. Relative kinetics were performed using various organic references and OH sources. After validation of the protocol, temperature-dependent rate constants for the reactions of OH radical with ethyl ter-butyl ether (, E_a/R=580 (±560) K), n-butyl acetate ( (±0.4)×10⁹ M⁻¹ s⁻¹, E_a/R=1000 (±200) K), acetone ( (±0.05)×10⁹ M⁻¹ s⁻¹, E_a/R=1400 (±500) K), methyl ethyl ketone (, E_a/R=1200 (±200) K), methyl iso-butyl ketone (, E_a/R=1200 (±300) K) and methylglyoxal (, E_a/R=1100 (±300) K) were determined. A non-Arrhenius behavior was found for phenol, in good agreement with the contribution of an OH addition to the mechanism, which also includes H-abstraction by OH radicals. Global rate constants of acetaldehyde, propionaldehyde, butyraldehyde and valeraldehyde were studied at 298 K only, as these compounds partly hydrate in the aqueous phase. All the obtained data (except those of phenol) complemented by literature data were used to investigate three methods to estimate rate constants for H-abstraction reactions of OH radicals in aqueous solutions when measured data were not available: Evans-Polanyi-type correlations, comparisons with gas-phase data, structure activity relationships (SAR). The results show that the SAR method is promising; however, the data set is currently too small to extend this method to temperatures other than 298 K. The atmospheric impact of aqueous phase OH oxidation of water-soluble organic compounds is discussed with the determination of their global atmospheric lifetimes, taking into account both gas- and aqueous-phase reactivities. The results show that atmospheric droplets can act as powerful photoreactors to eliminate soluble organic compounds from the atmosphere.     

Specific biomagnification of polychlorinated dibenzo-p-dioxins and dibenzofurans in tufted ducks (Aythya fuligula), common cormorants (Phalacrocorax carbo) and their prey from Lake Shinji, Japan

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/DFs) were detected in waterfowl such as common cormorants, tufted ducks, and their prey, namely fish and bivalves from Lake Shinji, Japan. The concentration of total PCDDs/DFs-TEQ was found to be higher in the muscle tissues of common cormorants than in those of tufted ducks. The results of hierarchical cluster analysis implied that the residue distribution pattern of PCDD/DF homologues was considerably different between these two species. Furthermore, biomagnification factors (BMFs) were estimated from bivalves as prey to tufted duck muscles as target organs. Despite the highest concentrations of 1,3,6,8- and 1,3,7,9-TeCDD in tufted ducks and their prey, however, the BMFs of these isomers were calculated to be lower than those of the toxic 2,3,7,8-substituted PCDDs/DFs. On the other hand, log BMF of toxic 2,3,7,8-substituted PCDDs/DFs were significantly higher for lower chlorinated isomers than those of the higher chlorinated isomers. The biota-sediment accumulation factors (BSAFs) of PCDDs/DFs were also estimated using shijimi clam and fish samples against sediment from Lake Shinji. The average BSAFs were estimated and ranged from 4.0×10⁻³ to 2.2×10⁻¹ and 2.0×10⁻⁴ to 2.0×10⁻¹ for bivalve and fish samples, respectively. Based on calculated BMFs and BSAFs, the total PCDD/DF-TEQ levels in the tufted duck were estimated to have been lowest (2.0 pg TEQ/g dry weight basis) in 1947 and highest (9.8 pg TEQ/g) in 1971.     

Emissions of organophosphate and brominated flame retardants from selected consumer products and building materials

The emissions of selected flame retardants were measured in 1- and 0.02-m³ emission test chambers and 0.001-m³ emission test cells. Four product groups were of interest: insulating materials, assembly foam, upholstery/mattresses, and electronics equipment. The experiments were performed under constant environmental conditions (23°C, 50% RH) using a fixed sample surface area and controlled air flow rates. Tris (2-chloro-isopropyl)phosphate (TCPP) was observed to be one of the most commonly emitted organophosphate flame retardants in polyurethane foam applications. Depending on the sample type, area-specific emission rates (SER_a) of TCPP varied between 20 ng m⁻² h⁻¹ and 140 μg m⁻² h⁻¹.The emissions from electronic devices were measured at 60°C to simulate operating conditions. Under these conditions, unit specific emission rates (SER_u) of organophosphates were determined to be 10–85 ng unit⁻¹ h⁻¹. Increasing the temperature increased the emission of several flame retardants by up to a factor of 500. The results presented in this paper indicate that emissions of several brominated and organophosphate flame retardants are measurable. Polybrominated diphenylethers exhibited an SER_a of between 0.2 and 6.6 ng m⁻² h⁻¹ and an SER_u of between 0.6 and 14.2 ng unit⁻¹ h⁻¹. Because of sink effects, i.e., sorption to chamber components, the emission test chambers and cells used in this study have limited utility for substances low vapour pressures, especially the highly brominated compounds; hexabromocyclododecane had an SER_a of between 0.1 and 29 ng m⁻² h⁻¹ and decabromodiphenylether was not detectable at all.     

Polychlorinated biphenyls in the Kupa River, Croatia, Yugoslavia

The presence of polychlorinated biphenyls (PCBs) was investigated in samples of water, suspended particles, sediments and fish from the Kupa river, Croatia, Yugoslavia, along a river stretch extending up to 10 km upstream and 200 km downstream of the primary contaminated karst region. Contamination was due to improper disposal of industrial waste discharge. The PCB levels detected in the samples collected downstream ranged from 1 to 52 ng 1⁻¹ for water, from 50 to 190 μg kg⁻¹ for suspended particles and from 8 to 39 μg kg⁻¹ for the sediment. A wide range of PCB concentrations, from 0.1 to 42.3 μg g⁻¹, which were measured in edible portions of different fish confirmed a long-term contamination of the river with PCBs. As the Kupa may be classified among low to moderately contaminated waters, it is essential that the investigations of the presence and behaviour of PCBs in the river and its environment be continued.     

Organochlorine pesticides and polybrominated diphenyl ethers in irrigated soils of Beijing, China: Levels, inventory and fate

Limited information on the levels, inventory and fate of Organochlorine pesticides (OCPs) and Polybrominated diphenyl ethers (PBDEs) in the soils irrigated by sewage or wastewater is available. In this study, variation in concentrations, profiles and fate of OCPs and PBDEs were investigated using soil samples collected from a region irrigated by sewage, mixed water and clean water in the east of Beijing, China. No significant variation was observed among groups, except for penta-BDEs. The measured ΣOCPs and ΣPBDEs residues ranged from 6.4 to 171.2 ng g⁻¹ (dw) and 501.9 to 3310.7 pg g⁻¹ (dw), respectively. ΣDDTs and BDE-209 were the most abundant congeners accounting for about 76% of ΣOCPs and 93% of ΣPBDEs. Concentrations of hexachlorocyclohexanes (HCHs), dichlorodiphenyltrichloroethane (DDTs) and its major degradation products, and hexachlorobenzene (HCB) ranged from 1.2 to 11.4 ng g⁻¹ (dw), 4.0 to 155.6 ng g⁻¹ (dw) and 0.3 to 3.4 ng g⁻¹ (dw), respectively. The major DDT degradation products were p,p′-DDT and p,p′-DDE. The major hexachlorocyclohexane (HCH) isomer in irrigated soils is β-HCH, reflecting its higher affinity to solids and resistance to degradation than other isomers. Both α-HCH/β-HCH and p,p′-DDT/p,p′-DDE ratios were log-normally distributed and negatively correlated to log(ΣHCHs) and log(ΣDDTs), respectively, suggesting no significant recent application of OCPs. Individual BDE congeners, ΣPBDEs and ΣOCPs were significantly correlated with total organic carbon (TOC). Moreover, a good correlationship between ΣPBDEs and black carbon (BC) was obtained but not between ΣOCPs and BC. Sewage irrigation did not have obvious effect on their contaminant levels and inventory of OCPs and PBDEs.     

The potential inhalation hazard posed by dioxin-contaminated soil

Conservative models were used to estimate the airborne concentrations of 2,3,7,8 tetrachlorodibenzo-p-dioxin (TCDD) vapor and particulates originating from soil containing 100 ppb TCDD. The upper-bound estimates were 3.25 pg/m³ of airborne TCDD vapor on-site and 0.51 pg/m³ for TCDD vapor 100 meters downwind. The TCDD air concentration on-site due to suspended particulate is estimated to be 1.4 pg/m³, based on a TSP level of 0.07 mg/m³. Assuming 70 years of continuous exposure to these concentrations, the upper-bound cancer risks determined from the Jury model were estimated to be 9.4 × 10⁻⁶ to 1.1 × 10⁻⁴ and 1.5 × 10⁻⁶ to 1.7 × 10⁻⁵ for inhalation of on- and off-site vapor, respectively, and 4.1 × 10⁻⁶ to 4.6 × 10⁻⁵ for dust inhalation. Since few sites have average soil concentrations as high as 100 ppb TCDD, this worst-case analysis indicates that inhalation will rarely, if ever, be a significant route of exposure to TCDD-contaminated soil. Experimental results support this claim and point to much lower risk estimates (8.4 × 10⁻⁹ to 9.9 × 10⁻⁸), suggesting that the parameters used in the Jury model are likely to overestimate the actual airborne levels of TCDD at contaminated sites.