A chemical and toxicological profile of Dutch North Sea surface sediments

Chemical and toxicological profiles were assessed in surface sediments (fraction <63 μm) from the southern North Sea. In extracts of freeze-dried samples, polybrominated biphenyl (PBB), Irgarol 1051 and phthalate concentrations were below the respective detection limits (except di(2-ethylhexyl)phthalate, which was between 170 and 3300 μg kg⁻¹ dry weight (dw)). Hexabromocyclododecane (HBCD) concentrations were between 0.8 and 6.9 μg kg⁻¹ dw, with highest concentrations at river mouths. Polybrominated diphenylethers (PBDE) concentrations were 0.4–0.6 μg kg⁻¹ dw, decabromodiphenylether (BDE209) 1–32 μg kg⁻¹ dw. The ratio BDE209/PCB153 was used as a tracer for recent emissions, and pointed towards a BDE209 source in the Western Scheldt’s upper estuary. PCBs and PAHs were between 0.19–4.7 and 2.6–200 μg kg⁻¹ dw respectively and generally had highest concentrations at near-shore locations and river mouths.

Responses in the Microtox broad-spectrum and the Mutatox genotoxicity assays were generally low, with near-shore locations giving higher responses. The umu-C genotoxicity and the ER-CALUX assay for estrogenicity showed no response, with the exception of one near-shore location (IJmuiden outer harbour, ER-CALUX).

Highest dioxin-like toxicity (DR-CALUX) was found at near-shore locations, in the outflow of the Rhine/Meuse estuary including a dumping site of harbour sludge. At the Oyster Grounds, DR-CALUX responses appeared to be linked to the occurrence of larger PAHs (4–6 rings). A new, non-destructive clean up procedure resulted in significantly higher DR-CALUX responses than the current protocol. The Dutch legislation on disposal of harbour sludge at sea, dictates the use of the conventional clean up procedure. Our results therefore indicate that probably more dioxin-like toxicity associated with harbour sludge is disposed off at sea than assumed.     

Methane fluxes from tundra soils and snowpack in the maritime Antarctic

Methane fluxes were measured from three exposed tundra sites and four snowpack sites on the Fildes Peninsula in the maritime Antarctic in the summertime of 2002. The average fluxes at two normal tundra sites were −15.3 μg m⁻² h⁻¹ and −14.3 μg m⁻² h⁻¹, respectively. The fluxes from tundra site with fresh penguin dropping addition showed positive values with the average of 36.1 μg m⁻² h⁻¹, suggesting that the deposition of fresh droppings greatly enhanced CH₄ emissions from the poor Antarctic tundra during penguin breeding periods. The summertime variation in CH₄ flux was correlated with surface ground temperature and the precipitation. The correlation between the flux and PT₀, which is the product of the precipitation and surface ground temperature, was quite strong. The diurnal cycle of CH₄ flux from the tundra soils was not obtained due to local fluky weather conditions. The fluxes through four snowpack sites were also obtained by the vertical CH₄ concentration gradient and their average fluxes were −46.5 μg m⁻² h⁻¹, −28.2 μg m⁻² h⁻¹, −46.4 μg m⁻² h⁻¹ and −17.9 μg m⁻² h⁻¹, respectively, indicating that tundra soils under snowpack also consume atmospheric CH₄ in the maritime Antarctic; therefore these fluxes could constitute an important part of the annual CH₄ budget for Antarctic tundra ecosystem.     

Mercury levels in sediments of central Mediterranean Sea: a 150+ year record from box-cores recovered in the Strait of Sicily

To evaluate the degree of anthropogenic mercury pollution, Hg contents have been measured for box-core sediments sampled along three nearshore–offshore transects in the Strait of Sicily and well constrained for their mineralogy, bulk geochemistry and TOC%. Hg values are generally low (from 15 to 70 μg kg⁻¹); however, depth profiles clearly display upcore rising concentrations (up to 202 μg kg⁻¹ near the SE Sicily coast) that are attributed to anthropogenic load. Based on ²¹⁰Pb chronology, these trends are more dramatic across the last 20–30 years. Geogenic influence is thought to explain some anomalies related to volcanic emission and geothermal activity. Combined effects due to eastward flowing of the Modified Atlantic Water (MAW) and sea bottom morphology drove major anthropogenic accumulation.     

Antimony content of macrofungi from clean and polluted areas

Species of macrofungi (mushrooms) were collected from clean areas and analyzed for their antimony content. These were compared to species collected from extremely polluted areas in the vicinity of a lead smelter and on mine and slag dumps. Antimony content was determined using long-term instrumental neutron activation analysis (INAA). Ectomycorrhizal and terrestrial saprobic macrofungi were examined. Antimony content of macrofungi from the clean areas was mostly less than 100 μg kg⁻¹ (dry mass). The highest concentrations (units of mg kg⁻¹) were found in various species of the ectomycorrhizal genera Chalciporus and Suillus. Antimony contents of macrofungi growing in the polluted areas were considerably higher. The highest content was found in a single collection of Chalciporus piperatus (1423 mg kg⁻¹).     

Feasibility of phosphate fertilizer to immobilize cadmium in a field

To reduce effectively cadmium (Cd) phytoextractability by phosphate fertilizer in Cd contaminated soil, fused and superphosphate (FSP) was applied at the rate of 0, 33.5 (recommendation level), 167.5, and 335 kg P ha⁻¹ for radish (Raphanus sativa L.). Unlike from what we expected, soil Cd extractability and Cd concentration in radish increased with increasing FSP application in the field. To determine the effect of FSP on Cd immobilization, FSP was mixed with the selected soil at the rate of 0, 200, 400, 800, and 1600 mg P kg⁻¹ and then incubated for 8 weeks. As observed in the field study, NH₄OAc extractable Cd concentration increased slightly with FSP addition up to 400 mg P kg⁻¹ and thereafter dramatically decreased upon increasing its application rate. Soil pH and negative charge were decreased at low level of FSP application up to 400 mg P kg⁻¹, but thereafter continually increased with increasing application level. This could be indirect evidence that net soil negative charge was increased by the specific adsorption of phosphate at the high rate of FSP application over 400 mg P kg⁻¹. The labile Cd fraction (water soluble and exchangeable + acidic fraction) increased with increasing FSP application by 400 mg P kg⁻¹ and thereafter gradually decreased with corresponding increase in unlabile fraction (oxidizable and residual fraction). Based on these results, FSP might be applied with a very high rate over 800 mg P kg⁻¹ to decrease Cd extractability in the selected field. However, this level is equivalent to 1440 kg P ha⁻¹, which is about 43 times higher than the recommendation levels for radish production and resulted in a significant increase in water soluble P concentration creating a new environmental problem. Therefore, the feasibility of FSP to reduce Cd extractability in the field is very low.     

Distribution of pesticides and heavy metals in trophic chain

Determination of triazines herbicides (atrazine and simazine) by high performance liquid chromatography (HPLC) in samples of trophic chain were worked out. Determination limits of 0.5 μg g⁻¹ for atrazine, 0.8 μg g⁻¹ for simazine with pesticides recovery of 70–77% in trophic chain samples were obtained. The content of simazine in soils was in range 1.72–57.89 μg g⁻¹, in grass 5–88 μg g⁻¹, in milk 2.32–15.29 μg g⁻¹, in cereals 10.98–387 μg g⁻¹, in eggs 30.14–59.48 μg g⁻¹, for fruits: 2.45–6.19 μg g⁻¹. The content of atrazine in soils was in range 0.69–19.59 μg g⁻¹, in grass 7.85–23.85 μg g⁻¹, in cereals 1.88–43.08 μg g⁻¹. Cadmium, lead and zinc were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES) in the same samples as atrazine and simazine. Determination limits for cadmium 5 × 10⁻³ μg g⁻¹, for lead 1 × 10⁻² μg g⁻¹, and for zinc 0.2 × 10⁻³ μg g⁻¹, were obtained. The content of cadmium in soil was in range 0.13–5.89 μg g⁻¹, in grass 114–627.72 × 10⁻³ μg g⁻¹, in milk 8.88–61.88 × 10⁻³ μg g⁻¹, in cereals 0.20–0.31 μg g⁻¹, in eggs 0.11–0.15 μg g⁻¹, in fruits 0.23–0.59 μg g⁻¹. The content of lead in soils was in range 0.57–151.50 μg g⁻¹, in grass 0.16–136.57 μg g⁻¹, in milk 1.16–3.74 μg g⁻¹, in cereals 1.05–5.47 μg g⁻¹, in eggs 5.79–55.87 μg g⁻¹, in fruits 21.00–87.36 μg g⁻¹. Zinc content in soil was in range 9.15–424.5 μg g⁻¹, in grass 35.20–55.87 μg g⁻¹, in milk 20.00–34.38 μg g⁻¹, in cereals 14.94–28.78 μg g⁻¹, in eggs 15.67–32.01 μg g⁻¹, in fruits 14.94–18.88 μg g⁻¹.

Described below extraction and mineralization methods for particular trophic chains allowed to determine of atrazine, simazine, cadmium, lead and zinc with good repeatability and precision. Emphasis was focused on liquid–liquid extraction and solid-phase extraction of atrazine and simazine from analysed materials, as well as, on monitoring the content of herbicides and metals in soil and along trophic chain. Higher concentration of pesticides in samples from west region of Poland in comparison to that of east region is likely related to common applying them in Western Europe in relation to East Europe. The content of metals strongly depends on samples origin (industry area, vicinity of motorways).     

Distribution of pesticides and bisphenol A in sediments collected from rivers adjacent to coral reefs

To investigate the deteriorating health of coral reefs in Okinawa, Japan, natural sediment samples were analyzed for diuron, Irgarol 1051, chlorpyrifos, and bisphenol A (BPA) which are hazardous to corals. Samples were analyzed by solid-phase extraction (SPE) followed by high-performance liquid chromatography with tandem mass spectrometry (LC–MS–MS). Although diuron and chlorpyrifos usage is only well recorded for farms and not for cities, these chemicals were detected in both rural and urban areas. Additionally, diuron concentration in urban areas was in some cases higher than in rural areas, which might be caused by greater consumption of these chemicals in home gardens in city areas. Irgarol 1051 was detected in downstream river areas, which are situated far from the source sites such as pier or fishery harbor (0.6–3.2 km). This result suggested that Irgarol 1051 could be transported from the river mouths to the sampling sites during flood tides. High BPA concentrations were associated with urban areas (<1.2–22.0 μg kg⁻¹), while low concentrations were associated with rural areas (nd–6.8 μg kg⁻¹). The river sediments under study are delivered to coral reefs in large quantity through runoff caused by typhoons and other heavy rains. The highly hazardous chemicals are carried into coral reefs on these sediments. Therefore, these hazardous chemical substances may already be influencing the coral reefs.     

Distribution of polycyclic aromatic hydrocarbons in agricultural soils in South Korea

The content and type of polycyclic aromatic hydrocarbons (PAH) in soils from paddy fields and upland areas in South Korea were determined using gas chromatography linked to mass spectrometry (GC–MS). The distribution map of total PAH content was obtained as a contour plot using a geographical information system. The overall distribution of PAH was found to be closely related to the pollution sources, the size of city and the type of industry. The average content of total PAH in all samples was 236 μg kg⁻¹, and the range was from 23.3 to 2834 μg kg⁻¹. The highest concentrations were found in soils sampled near iron processing plants. The concentration of PAH decreased in the order fluoroanthene>benzo(b)fluoroanthene>pyrene. Special PAH compound ratios, such as phenanthrene/anthracene and fluoroanthene/pyrene, were calculated to evaluate the origin. The collected data suggested that the pyrogenic origins such as motor vehicle exhaust and heavy industry emission were the dominant source of PAH in Korean soils.     

Leaching and degradation of 21 pesticides in a full-scale model biobed

Filling and cleaning of pesticide sprayers presents a potential risk of pollution of soil and water. Three different solutions for handling sprayers have been suggested: Filling and cleaning in the field, filling and cleaning on hard surfaces with collection of the waste water, and filling and cleaning on a biobed, which is an excavation lined with clay and filled with a mixture of chopped straw, sphagnum and soil with turf on top, and with increased sorption capacity and microbial activity for degradation of the pesticides. In the present study the degradation and leaching of 21 pesticides (5 g of each) was followed in an established full-scale model biobed. Percolate was collected and analysed for pesticide residues, and the biobed material was sampled at three different depths and analysed by liquid chromatography double mass spectrometry (LC-MSMS). During the total study period of 563 days, no traces of 10 out of 21 applied pesticides were detected in the percolate (detection limits between 0.02 and 0.9 μg l⁻¹) and three pesticides were only detected once and at concentrations below 2 μg l⁻¹. During the first 198 days before second application, 14% of the applied herbicide bentazone was detected in the leachate with maximum and mean concentrations of 445 and 172 μg l⁻¹, respectively. About 2% of the initial mecoprop and fluazifop dose was detected in the percolate, with mean concentrations of 23 μg l⁻¹, while MCPA and dimethoate had mean concentrations of 3.5 and 4.7 μg l⁻¹, respectively. Leachate concentrations for the remaining pesticides were generally below the detection limit (0.02–0.9 μg l⁻¹, below 1% of applied). Sorption studies of five pesticides showed that compounds with a low K_d value appeared in the leachate. After 169 days, all pesticides in the biobed profile were degraded to a level below 50% of the calculated initial dose. Pesticides with K_oc values above 100 were primarily found in the uppermost 10 cm and degraded slowest due to the low bioavailability. The 11 most degradable pesticides were all degraded such that less than 3% remained in the biobed after 169 days.

Following second pesticide application of the biobed, leachate was sampled 215 and 365 days after the treatment. This showed the same pesticides to be leached out and at concentrations comparable to those of the first treatment. The same pesticides as after the first treatment were retained in the biobed.     

Methane emission characteristics and its relations with plant and soil parameters under irrigated rice ecosystem of northeast India

Methane flux from rice varieties grown under two identical soils of Assam were monitored. In the first experiment, variety Jaya and GRT was grown in sandy loam soil of Lower Brahmaputra Valley Zone of Assam and the second experiment was conducted with variety Jyotiprasad and Bishnuprasad in sandy to sandy loam soils of Upper Brahmaputra Valley Zones of Assam. Methane flux recorded from variety Jyotiprasad and GRT was higher compared to variety Bishnuprasad and Jaya. The seasonal integrated flux recorded was 10.76 g m⁻², 9.98 g m⁻², 9.74 g m⁻² and 11.31 g m⁻² for variety GRT, Jaya, Bishnuprasad and Jyotiprasad, respectively. All the varieties exhibited two methane peaks one at maximum tillering stage and other at panicle initiation stage of the crop. Crop growth parameters such as leaf number, number of tillers and leaf area index (LAI) showed strong positive relationship with total methane flux. In both the experiments it was calculated that CH₄ emission was substantially influenced by crop phenology and growth. This study emphasise the relationship of different growth parameters with methane emission.     

Mercury deposition through litterfall in an Atlantic forest at Ilha Grande, Southeast Brazil

Atmospheric Hg transfer to the forest soil through litterfall was investigated in a primary rainforest at Ilha Grande (Southeast Brazil) from January to December 1997. Litter mass deposition reached 10.0 t ha⁻¹ y⁻¹, with leaves composing 50–84% of the total litter mass. Concentrations of Hg in the total fallen litter varied from 20 to 244 ng g⁻¹, with higher concentrations during the dry season, between June and August (225 ± 17 ng g⁻¹), and lower concentrations during the rainy season (99 ± 54 ng g⁻¹). This seasonal variability was reflected in the Hg flux through litterfall, which corresponded to a Hg input to the forest floor of 122 μg m⁻² y⁻¹, with average Hg deposition of 16.5 ± 1.5 μg m⁻² month⁻¹ during and just after the dry season (June–September) and 7.0 ± 3.6 μg m⁻² month⁻¹ in the rest of the year. The variability in meteorological conditions (determining atmospheric Hg availability to foliar scavenging) may explain the pulsed pattern of Hg deposition, since litterfall temporal variability was generally unrelated with such deposition, except by a peak in litterfall production in September. Comparisons with regional data on Hg atmospheric deposition show that litterfall promotes Hg deposition at Ilha Grande two to three orders of magnitude higher than open rainfall deposition in non-industrialized areas and approximately two times higher than open rainfall deposition in industrialized areas in Rio de Janeiro State. The observed input suggests that atmospheric Hg transfer through litterfall may explain a larger fraction of the total Hg input to forest soils in Southeast Brazil than those recorded at higher latitudes.     

The enhancement of photodegradation efficiency using Pt-TiO2 catalyst

The residues from the extraction of lead/zinc (Pb/Zn) ores of most Pb/Zn mines are permanently stored in tailings ponds, which require revegetation to reduce their environmental impact. This can only be done if the main constraints on plant establishment are evaluated. This can readily be done by field and greenhouse studies.

To test this, the properties of different tailings from Lechang Pb/Zn mine located at the north of Guangdong Province in southern China have been studied. Physical and chemical properties including concentrations of metals (Pb, Zn, Cd and Cu) in the tailings and soils collected from different sites have been measured. The results showed that tailings contain low nitrogen (0.016–0.075%), low-organic matter (0.58–1.78%), high salt (3.55–13.85 dS/m), and high total and diethylene–tetramine–pentaacetic acid (DTPA)-extractable metal concentrations (total: 1019–1642 μg g⁻¹ Pb, 3078–6773 μg g⁻¹ Zn, 8–23 μg g⁻¹ Cd, and 85–192 μg g⁻¹ Cu; DTPA-extractable: 59–178 μg g⁻¹ Pb, 21–200 μg g⁻¹ Zn, 0.30–1.5 μg g⁻¹ Cd, and 4.3–12 μg g⁻¹ Cu). Aqueous extracts of tailings/soils (10%, 20% and 30%, w/v) from different sites were prepared for testing their effects on seed germination and root elongation of a vegetable crop Brassica chinensis and a grass species Cynodon dactylon. It was found that root elongation provided a better evaluation of toxicity than seed germination. The ranking of toxicity using root elongation was: high-sulfur tailings>tailingdam>sparsely vegetated tailings>densely vegetated tailings>mountain soil for both plants. This order was consistent with DTPA-extractable Pb contents in the tailings and soils. B. chinensis seedlings were then grown in the mixtures of different proportions of tailings and farm soil for 4 weeks, and the results (dry weights of seedlings) were in line with the root elongation test. All these demonstrated that heavy metal toxicity, especially available Pb, low content of nutrient, and poor physical structure were major constraints on plant establishment and colonization on the Pb/Zn mine tailings.     

Direct measurement of denitrification activity in a Gulf coast freshwater marsh receiving diverted Mississippi River water

Wetland loss along the Louisiana Gulf coast and excessive nitrate loading into the Gulf of Mexico are interrelated environmental problems. Nitrate removal by soil denitrification activity was studied in a ponded freshwater marsh receiving diverted Mississippi River water for the purpose of reversing or slowing wetland loss. Labeled ¹⁵N-nitrate was applied at 3.8 g N m⁻² into four replicate study plots after removing above ground vegetation. Nitrogen gas (N₂) and nitrous oxide (N₂O) emissions from the plots were determined by isotope ratio mass spectrometry (IRMS). Nitrous oxide emissions were also compared with the results determined by gas chromatograph (GC). Results showed that it took 2 weeks to remove the added nitrate with N₂O emission occurring over a period of 4 d. The apparent denitrification dynamics were assumed to follow the Michaelis–Menten equation. The maximum denitrification rate and K_m value were determined as 12.6 mg N m ⁻² h⁻¹, and 6.5 mg N l⁻¹, respectively. Therefore the maximum capacity for nitrate removal by the marsh soil would be equivalent to 110 g N m⁻² yr⁻¹, with more than 30% of nitrogen gas evolved as N₂O. For typical nitrate concentrations in Mississippi River water of about 1 mg N l⁻¹, nitrate would be removed at a rate of 14.7 g N m⁻² yr⁻¹ with N₂O emission about 1.5%. A denitrification dynamic model showed that the efficiency of nitrate removal would largely depend on the water discharge rate into the ponded wetland. Higher discharge rate will result in less retention time for the water in the marsh where nitrate is denitrified.     

Determination and distribution characteristics of degradation products of nonylphenol polyethoxylates in the rivers of Taiwan

Concentrations of degradation products of nonylphenol polyethoxylates (NPEOs) were analyzed in river water samples in order to determine the distribution characteristic of these alkylphenolic compounds in 18 major rivers of Taiwan. The degradation products of NPEOs were detected in all river samples, with the dicarboxylates alkylphenolic degradation products (CAPEC) being detected most frequently and at the highest concentrations. Concentrations of NP and NP1EO in rivers ranged from n.d. to 5.1 μg l⁻¹ and n.d. to 0.5 μg l⁻¹, respectively. The total concentrations of shortened carboxylates (i.e., NP1EC + NP2EC + NP3EC) and dicarboxylates alkylphenolic degradation products (CAP1EC + CAP2EC) ranged from n.d. to 63.6 μg l⁻¹ and n.d. to 94.6 μg l⁻¹, respectively. Concentrations of NP2EC, NP3EC and all CAPEC residues were determined semi-quantitatively by comparing with the internal standard. Significantly higher concentrations of CAPEC residues were detected in the river waters as compared to those of NP, NP1EO and NPEC degradation products and the average proportions of these compounds in the samples of the rivers were as follows: NP + NP1EO was 5 ± 2.5%, total NPEC was 25 ± 12%, and total CAPEC was 70 ± 12%. The high concentration ratios of CAPEC/NPEC illustrate that aerobic biodegradation plays a main route in the fate of NPEO in the rivers of Taiwan.     

Efficient removal and mechanisms of water soluble aromatic contaminants by a reduced-charge bentonite modified with benzyltrimethylammonium cation

A novel strategy utilizing the phenyls interaction and the hydrophobic affinity of available siloxane surface in the interlayer of bentonite was proposed to improve the sorption capabilities of organobentonites for water soluble aromatic contaminants. A unique organobentonite (65BTMA) was synthesized by intercalating benzyltrimethylammonium cation (BTMA⁺) into the interlayer of a reduced-charge bentonite with cation exchange capacity (CEC) of 65 cmol kg⁻¹. Phenol, aniline and toluene were used as model compounds of water soluble aromatic contaminants. Their respective removal efficiencies by 65BTMA were achieved at 83.3%, 89.2% and 97.3% at the initial concentration of 20 mg l⁻¹. To reveal the sorption mechanism, sorption characteristics of aromatic contaminants to 65BTMA were compared with that of aliphatic contaminants in similar molecular size. And various organobentonites were prepared by combining TMA⁺ (tetramethylammonium), BTMA⁺, HTMA⁺ (heptyltrimethylammonium) and CTMA⁺ (cetyltrimethylammonium) with two bentonites (CEC = 108 and 65 cmol kg⁻¹). To 65BTMA, sorption magnitudes of aromatic contaminants were much greater than that of aliphatic compounds with similar size; and dramatically higher than those to other organobentonites at low pollutant concentrations. These observations revealed that the strong phenyls interactions contributed significantly to sorb the aqueous soluble aromatic contaminants to 65BTMA (>90%), and which favored to design uniquely powerful sorbents.     

An assessment of the risks associated with PCDDs and PCDFs following the application of sewage sludge to agricultural land in the UK

A model has been developed to describe the transfer of PCDDs and PCDFs from sludge-amended soils to the human foodchain. The model is conservative and assumes that all foods consumed by an individual are derived from sludge-amended soils. Predicted concentrations of PCDDs and PCDFs in potatoes, cereals, root vegetables and leafy vegetables were in close agreement with mean concentrations reported in the food survey conducted by MAFF in the UK. Predicted concentrations in milk were well below the Maximum Tolerable Concentration adopted by MAFF. Assuming a half-life of ten years in sludge-amended soils, the maximum estimated incremental daily intake (IDI) predicted by the model following ten applications of sludge to agricultural land was 0.80 pg I-TEQ kg⁻¹ day⁻¹, representing an increase of approximately 45% on current levels of background exposure. For an individual whose diet is solely derived from sludge-amended soils, the total exposure is predicted to be approximately 181 pg I-TEQ day⁻¹ or 2.6 pg I-TEQ kg⁻¹ day⁻¹. This compares with an average background exposure of approximately 2 pg I-TEQ kg⁻¹ day⁻¹, well within the TDI of 10 pg I-TEQ kg⁻¹ day⁻¹ and indicates that the application of sewage sludge to agricultural land under the conditions assumed would not appear to present a significant health risk under the conservative scenarios considered in this assessment.     

Octyl and nonylphenol ethoxylates and carboxylates in wastewater and sediments by liquid chromatography/tandem mass spectrometry

This work presents an LC–MS–MS-based method for the quantitation of nonylphenol ethoxylates (NPEOs) and octylphenol ethoxylates (OPEOs) in water, sediment, and suspended particulate matter, and three of their carboxylated derivatives in water. The alkylphenol ethoxylates (APEOs) were analyzed using isotope dilution mass spectrometry with [¹³C₆]-labeled analogues, whereas the carboxylated derivatives were determined by external standard quantitation followed by confirmation using standard additions. The method was used to study APEO’s behavior in a wastewater treatment plant (WWTP), where total dissolved NP0-16EO concentration was reduced by approximately 99% from influent (390 μg l⁻¹) to final effluent (4 μg l⁻¹), and total OP0-5EO concentration decreased by 94% from 3.1 to 0.2 μg l⁻¹. In contrast, the carboxylated derivatives were formed during the process with NP0-1EC concentrations increasing from 1.4 to 24 μg l⁻¹. Short-chain APEOs were present in higher proportions in particulate matter, presumably due to greater affinity for solids compared to the long-chain homologues. NP (0.49 μg l⁻¹) and NP0-1EC (4.8 μg l⁻¹) were the only APEO-related compounds detected in a surface water sample from a WWTP-impacted estuary; implying that 90% of the mass was in the form of carboxylated derivatives. Sediment analysis showed nonylphenol to be the single most abundant compound in sediments from the Baltimore Harbor area, where differences in homologue distribution suggested the presence of treated effluent in some of the sites and non-treated sources in the rest.     

Isoprene emission from tropical trees in Okinawa Island, Japan

This study surveyed isoprene emission from 42 indigenous and exotic tropical trees in subtropic Okinawa, Japan. Of the 42 trees studied, 4 emitted isoprene at a rate in excess of 20 μg g⁻¹ h⁻¹, and 28 showed the rates of 1–10 μg g⁻¹ h⁻¹. The remainder emitted less than 1 μg g⁻¹ h⁻¹. The majority of trees in this study may therefore fall within the lower emitting species. However, species in Moraceae that is indigenous in Okinawa emitted isoprene at relatively higher rates with an average of 14.2 μg g⁻¹ h⁻¹. The highest emission rate of 107.1 μg g⁻¹ h⁻¹ for Ficus virgata yielded the area basis rate of 47.4 nmol m⁻² s⁻¹, which is almost equivalent to the rate of high emitting species. Furthermore, a linear relationship between light intensity and isoprene emission was noted with Ficus virgata up to 1700 μmol m⁻² s⁻¹. These findings may show the potential importance of subtropical areas as sources of isoprene to the atmosphere.     

Trace elements in atmospheric particulate matter over a coal burning power production area of western Macedonia, Greece

Total suspended particle (TSP) concentrations were determined in the Eordea basin (western Macedonia, Greece), an area with intensive lignite burning for power generation. The study was conducted over a one-year period (November 2000–November 2001) at 10 sites located at variable distances from the power plants. Ambient TSP samples were analyzed for 27 major, minor and trace elements. Annual means of TSP concentrations ranged between 47 ± 33 μg m⁻³ and 110 ± 50 μg m⁻³ at 9 out of the 10 sites. Only the site closest to the power stations and the lignite conveyor belts exhibited annual TSP levels (210 ± 97 μg m⁻³) exceeding the European standard (150 μg m⁻³, 80/779/EEC). Concentrations of TSP and almost all elemental components exhibited significant spatial variations; however, the elemental profiles of TSP were quite similar among all sites suggesting that they are affected by similar source types. At all sites, statistical analysis indicated insignificant (P < 0.05) seasonal variation for TSP concentrations. Some elements (Cl, As, Pb, Br, Se, S, Cd) exhibited significantly higher concentrations at certain sites during the cold period suggesting more intense emissions from traffic, domestic heating and other combustion sources. On the contrary, concentrations significantly higher in the warm period were found at other sites mainly for crustal elements (Ti, Mn, K, P, Cr, etc.) suggesting stronger influence from soil resuspension and/or fly ash in the warm months. The most enriched elements against local soil or road dust were S, Cl, Cu, As, Se, Br, Cd and Pb, whereas negligible enrichment was found for Ti, Mn, Mg, Al, Si, P, Cr. At most sites, highest concentrations of TSP and elemental components were associated with low- to moderate-speed winds favoring accumulation of emissions from local sources. Influences from the power generation were likely at those sites located closest to the power plants and mining activities.     

Selective adsorption of phenanthrene dissolved in surfactant solution using activated carbon

Selective adsorption of a hazardous hydrophobic organic compound (HOC) by activated carbon as a means of recovering surfactants after a soil washing process was investigated. As a model system, phenanthrene was selected as a representative HOC and Triton X-100 as a nonionic surfactant. Three activated carbons that differed in size (Darco 20–40 (D20), 12–20 (D12) and 4–12 (D4) mesh sizes) were used in adsorption experiments. Adsorption of surfactant onto activated carbon showed a constant maximum above the critical micelle concentration, which were 0.30, 0.23, 0.15 g g⁻¹ for D20, D12, and D4, respectively. Selectivity for phenanthrene to Triton X-100 was much higher than 1 over a wide range of activated carbon doses (0–6 g l⁻¹) and initial phenanthrene concentrations (10–110 mg l⁻¹). Selectivity generally increased with decreasing particle size, increasing activated carbon dose, and decreasing initial concentration of phenanthrene. The highest selectivity was 74.9, 57.3, and 38.3 for D20, D12, and D4, respectively, at the initial conditions of 10 mg l⁻¹ phenanthrene, 5 g l⁻¹ Triton X-100 and 1 g l⁻¹ activated carbon. In the case of D20 at the same conditions, 86.5% of the initial phenanthrene was removed by sorption and 93.6% of the initial Triton X-100 remained in the solution following the selective adsorption process. The results suggest that the selective adsorption by activated carbon is a good alternative for surfactant recovery in a soil washing process.