Toxicity of three halogenated flame retardants to nitrifying bacteria, red clover (Trifolium pratense), and a soil invertebrate (Enchytraeus crypticus)

Halogenated flame retardants have a high sorption affinity to particles, making soils and sediments important sinks. Here, three of the most commonly used flame retardants have been tested for sub-lethal toxicity towards soil nitrifying bacteria, a terrestrial plant (seed emergence and growth of the red clover, Trifolium pratense), and a soil invertebrate (survival and reproduction of Enchytraeus crypticus). Tetrabromobisphenol A (TBBPA) was quite toxic to enchytraeids, with significant effects on reproduction detected already at the 10 mgkg(-1) exposure level (EC(10)=2.7 mgkg(-1)). In contrast, decabromodiphenyl ether (DeBDE) was not toxic at all, and short-chain chloroparaffins (CP(10-13)) only affected soil nitrifying bacteria at the highest test concentration (EC(10)=570 mgkg(-1)). Exposure concentrations were verified by chemical analysis for TBBPA and DeBDE, but not for CP(10-13), as a reliable method was not available. Based on the generated data, a PNEC for soil organisms can be estimated at 0.3 mgkg(-1) for TBBPA and 57 mgkg(-1) for short-chain chloroparaffins. No PNEC could be estimated for DeBDE. Measurements of TBBPA in soil are not available, but measured concentrations in Swedish sludge are all lower than the estimated threshold value for biological effects in soil.     

Arbuscular mycorrhiza enhanced arsenic resistance of both white clover (Trifolium repens Linn.) and ryegrass (Lolium perenne L.) plants in an arsenic-contaminated soil

In a compartmented cultivation system, white clover (Trifolium repens Linn.) and ryegrass (Lolium perenne L.), with their roots freely intermingled, or separated by 37 microm nylon mesh or plastic board, were grown together in an arsenic (As) contaminated soil. The influence of AM inoculation on plant growth, As uptake, phosphorus (P) nutrition, and plant competitions were investigated. Results showed that both plant species highly depended on mycorrhizas for surviving the As contamination. Mycorrhizal inoculation substantially improved plant P nutrition, and in contrast markedly decreased root to shoot As translocation and shoot As concentrations. It also showed that mycorrhizas affected the competition between the two co-existing plant species, preferentially benefiting the clover plants in term of nutrient acquisition and biomass production. Based on the present study, the role of AM fungi in plant adaptation to As contamination, and their potential use for ecological restoration of As contaminated soils are discussed.     

The effect of ryegrass (Lolium perenne) on decrease of PAH content in long term contaminated soil

The biodegradation of polycyclic aromatic hydrocarbons in microecosystems containing long-term contaminated soil was investigated. Soil was contaminated by different chemicals, including PAHs since World War II. Aging of the soil was expected to act as a principal factor limiting biodegradation. Half of the microecosystems contained ryegrass (Lolium perenne) and long-term selected natural soil microflora originally present in contaminated soil. The others contained contaminated soil with natural microflora only. Half of the microecosystems in each parallel experiment was fertilised with N-P-K fertiliser. Cultivation was carried out at 12 and 18 months in a greenhouse with a natural photoperiod and the ability to degrade 15 chosen PAH was investigated. For analysis, the soil from each pot was divided into three horizontal layers for mutual comparison among layers and each layer was further divided into four equal samples. Soil extracts were analysed using HPLC. After a one-year-cultivation period the content of the monitored PAHs declined to 50%. Mostly, there were no significant differences between the microecosystems. Best degraded were fluoranthene and pyrene, which were the major contaminants present in original soil. Also, other compounds were successfully degraded, even benzo[a]pyrene and benzo[ghi]perylene. Dibenz[a,h]anthracene and indeno[1,2,3-cd]pyrene were the only PAHs, examined that showed no significant degradation. Although some differences between the soil layers were detected, no conclusive trends could be found. However, significantly lower concentrations of PAHs were determined mostly in the bottom layer of the analysed profiles. In vegetated microecosystems the decline of PAHs concentrations was more remarkable after 18 months cultivation.     

Elemental analysis and nutritional value of edible Trifolium (clover) species

Trifolium species, commonly known as clover species, have a cosmopolitan distribution and, as such, are used in many different traditional systems of medicine and consumed by many communities all over the world. In this study, the elemental distribution and nutritional value of five edible Trifolium species, namely, Trifolium africanum, Trifolium burchellianum, Trifolium repens, Trifolium dubium and Trifolium pratense were investigated to evaluate the potential of these plant species to alleviate malnutrition, thereby contributing toward the fight against food insecurity. Trifolium species were found to be a rich alternate source of essential nutrients with concentrations of elements being in decreasing order of Ca > Mg > Fe > Mn > Zn > Se > Cu > Cr > Pb > Ni > Co > Cd > As and with adequate levels of lipids (4.2 to 8.6%), proteins (35.1 to 45.4%) and carbohydrates (26.7 to 47.0%). Trifolium species were found to be rich in Se (contributing greater than 516% toward its RDA) with T. dubium having a concentration of 0.53 mg 10 g^?1, dry mass, which is higher than Brazil nuts. T. pratense was found to be the most suitable species for human consumption due to it having low levels of toxic metals (As, Cd and Pb) while being rich in macro- and micro-elements, especially Fe (7.84 mg 10 g^?1, dry mass) and Se (0.36 mg 10 g^?1, dry mass).     

Effect of in situ soil amendments on arsenic uptake in successive harvests of ryegrass (Lolium perenne cv Elka) grown in amended As-polluted soils

Several iron-bearing additives, selected for their potential ability to adsorb anions, were evaluated for their effectiveness in attenuation of arsenic (As) in three soils with different sources of contamination. Amendments used were lime, goethite (alpha-FeOOH) (crystallised iron oxide) and three iron-bearing additives, iron grit, Fe(II) and Fe(III) sulphates plus lime, applied at 1% w/w. Sequential extraction schemes conducted on amended soils determined As, Cu, Zn and Ni fractionation. Plant growth trials using perennial ryegrass (Lolium perenne var. Elka) assessed shoot As uptake. This was grown in the contaminated soils for 4 months, during which time grass shoots were successively harvested every 3 weeks. Goethite increased biomass yields, but clear differences were observed in As transfer rates with the various iron oxides. In conclusion, whilst Fe-oxides may be effective in situ amendments, reducing As bioavailability, their effects on plant growth require careful consideration. Soil-plant transfer of As was not completely halted by any amendment.     

Residues of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides in organically-farmed vegetables

The residues of polyaromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in soils from organic farms and their uptake by four varieties of organic-produced potatoes and three varieties of organic carrots from England were investigated. Samples of the soils, crop peels and cores were all Soxhlet-extracted in triplicate, cleaned up by open-column chromatography and analysed by a multi-residue analytical method using gas chromatography with mass selective detection. The concentrations of PAHs, PCBs and OCPs in soils from organic farms ranged from 590+/-43 to 2301+/-146 microg/kg, 3.56+/-0.73 to 9.61+/-1.98 microg/kg and 52.2+/-4.9 to 478+/-111 microg/kg, respectively. Uptake by different crop varieties were 8.42+/-0.93 to 40.1+/-4.9 microg/kg sigmaPAHs, 0.83+/-0.19 to 2.68+/-0.94 microg/kg sigmaPCBs and 8.09+/-0.83 to 133+/-27 microg/kg sigmaOCPs. Residue uptake from soils depended on plant variety; Desiree potato and Nairobi carrot varieties were more susceptible to PAH contamination. Likewise, uptake of PCBs and OCPs depended on potato variety. There were significant positive correlations between the PCB and OCP concentrations (P<0.05) in soils and carrots but no significant correlation was found between the concentrations of any contaminants in soils and potatoes. Peeling carrots and potatoes was found to remove 52-100% of the contaminant residues depending on crop variety and the properties of the contaminants. Soil-crop bioconcentration factors (BCFs) decreased with increasing logK(ow) for PAHs up to about 4.5 and for PCBs up to about 6.5, above which no changes were discernible for either class of contaminants. No relationship was observed between soil-crop BCFs and logK(ow) for OCPs, most likely because their concentrations were low and variable.     

Sorption of polycyclic aromatic hydrocarbons (PAHs) to low and high density polyethylene (PE)

Background, aim, and scope

According to their high sorption capacity polyethylene (PE) passive samplers are often used for the analysis of polycyclic aromatic hydrocarbons (PAHs) in the aquatic environment. PE is also one of the primary synthetic polymers found in oceans, and sorption of PAHs to marine PE debris may determine PAH exposure and therefore hazards in marine ecosystems. Thus, an understanding of the sorption process is of great importance. In the present study, the sorption of several PAHs with different polarities to low density polyethylene (LDPE) and high density polyethylene (HDPE) was studied in order to improve our understanding of the influence of material properties on the Fickian diffusion of PAHs into PE.

Materials and methods

Batch sorption experiments were performed with aqueous solutions containing acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, and LPDE or HDPE pellets. Samples were shaken in the dark at 20?±?1°C for 16 time intervals within one week. Concentrations of PAHs were determined in the aqueous samples using solid-phase microextraction coupled with gas chromatography–mass spectrometry. The distribution coefficients (K _PE) between PE and water were estimated from different models reported in the literature. Kinetic sorption of the PAHs into the plastic pellets was described by a diffusion model based on Fick’s second law in spherical coordinates.

Results and discussion

A comparison between different models describing the equilibrium distribution of PAHs between PE and water revealed that the sorption equilibrium seemed to be driven by parameters other than, or in addition to, organic carbon. For both plastic types, diffusion coefficients decreased while the molecular weight of the PAHs increased which indicates a hindered diffusion through the matrix as a result of a larger molecule size. Higher diffusion coefficients were derived for LPDE than for HDPE indicating a greater sorption velocity for LPDE according to the lower polymer density.

Conclusions

Our results revealed that equilibrium time could be shortened during passive sampling as polymer membranes of lower density are used. In some areas, marine ecosystems may not be in equilibrium with respect to concentrations of organic contaminants and abundance of marine plastic debris. In such cases, different polymer densities should be taken into account in risk assessments.

     

The effects of soil and Trifolium repens (white clover) on the fate of estrogen

In this study, we investigated the behavior of estrogens in the rhizosphere of white clover (Trifolium repens, clover hereafter) with two different pot tests, using soil and agar as growth media. In a pot test using agar spiked with estrogen, the estrogen concentration in the agar with clover decreased to non-detectable levels within one month, while in the agar without clover, 60% of initially added estrogen remained after one month. The half-lives of estrone (E1) and 17β -estradiol (E2) in the agar with clover were 2.4–3.8 and 13.2 d, respectively. The dissipation of E1 followed first-order rate law, while that of E2 fitted a zero-order reaction, indicating that they had different mechanisms of dissipation from agar. In the soil pot test, the behavior of E1 and E2 was not influenced by clover. An initial rapid decrease in the amount of estrogen extracted by methanol/acetic acid was followed by persistence for 1–3 months, regardless of presence of clover. Moreover, in three weeks E1 and E2 were only partly degraded by microbes extracted from the soil used in the pot test. In this study, abiotic degradation of estrogens and sorption of estrogen to soil, rather than the effects of soil microbes and clover, contributed to the initial rapid dissipation of estrogens in the soil. However, the results of the agar pot test suggested that vegetation such as clover may significantly contribute to removal of estrogens when estrogens in aqueous phase are discharged with surface runoff and preferential flow after heavy rain in agricultural fields, or when present in soils with low estrogen sorptivity.     

Polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), biphenyls (PCBs), and polycyclic aromatic hydrocarbons (PAHs) and 2,3,7,8-TCDD equivalents (TEQs) in sediment from the Hyeongsan River, Korea

Sediment, pore water and water samples from the Hyeongsan River, Korea were analyzed for several classes of halogenated aromatic hydrocarbons (HAHs) and their dioxin-like activities were evaluated using the in vitro H4IIE-luc bioassay. Polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), and biphenyls (PCBs) were detected in sediments from all six sampling locations with mean concentrations of 2.8 x 10(2) pg/g, 190 pg/g, and 61.4 ng/g, dw, respectively. Polycyclic aromatic hydrocarbons (PAHs) were predominated by 4-6 ring compounds with concentrations in the range of 5.30-7680 ng/g, dw. Chemical profiles of target analytes in sediment and water samples revealed that there was a gradient of concentrations along the river from upstream to downstream, which suggested that the primary source was a wastewater reservoir adjacent to a sewage treatment plant (STP). TEQs derived by summing the product of concentrations of individual congeners by their respective relative potencies (REPs or TEFs) ranged from 4.3 x 10(-1) to 1.1 x 10(3) pg/g, dw. Raw Soxhlet extracts from all six sampling locations induced significant dioxin-like responses in the H4IIE-luc bioassay. TCDD-EQs derived from H4IIE bioassay ranged from 7 x 10(-3) to 1.5 x 10(3) pg/g, dw, which were significantly correlated with TEQs (r2 = 0.994, p < 0.05). Among the three Florisil fractions tested, PCDD/Fs in fraction (F2) induced the greatest magnitude of response (range: 24-83%-TCDD-max.) in the H4IIE-luc assay. Comparison of the TEQ and TCDD-EQ suggested little non-additive interaction between fractions and AhR-active and inactive compounds. Concentrations of individual congeners as well as TEQs and TCDD-EQs suggest inputs from the industrial center waste stream in the Hyeongsan River.     

Permanganate oxidation of polycyclic aromatic compounds (PAHs and polar PACs): column experiments with DNAPL at residual saturation

Environmental Science and Pollution Research - Permanganate is an oxidant usually applied for in situ soil remediation due to its persistence underground. It has already shown great efficiency for...     

Accumulation and distribution of polycyclic aromatic hydrocarbons in rice (Oryza sativa)

Various tissues of rice plants were sampled from a PAH contaminated site in Tianjin, China at different growth stages of the ripening period and analyzed for PAHs. PAHs were much higher in roots than in the exposed tissues. Grains and internodes accumulated much smaller amounts of PAHs than leaves, hulls or ear axes. No specific gradient trends along roots, stem, ear axes, and grains were observed, suggesting that systematic translocation among them is unlikely. Over the ripening period, PAH concentrations were increased in rice roots and decreased in most above-ground tissues. Significant correlations between PAH and lipid contents can only be observed during full mature stage. The spectra of individual PAH compounds in rice organs including roots were similar to those in air, rather than those in soil. There was also a significant correlation between bioconcentration factor (BCF, plant over air) and octanol/air partitioning coefficient (Koa).     

Sorption of polycyclic aromatic hydrocarbons (PAHs) to carbonaceous materials in a river floodplain soil

We report on sorption isotherm of phenanthrene (Phe) for river floodplain soil associated with carbonaceous materials, with particular attention being devoted to the natural loading of Phe. Our sorption experiments with original soil samples, size, and density sub-fractions showed that the light fraction had the highest sorption capacity comparable to low rank coals. In addition, the light fraction contributed most for the sorption of Phe in total soil samples. K_oc values for all fractions were in the same range, thus indicating that coal and coal-derived particles in all samples are responsible for the enhanced sorption for Phe. Sorption was strongly nonlinear and the combined partitioning and pore-filling model gave a better fit than the Freundlich sorption model. In addition, the spiked PAHs did not show the same behavior as the naturally aged ones, therefore the accessibility of indigenous background organic contaminants was reduced when coal and coal-derived particles are associated with the soils.     

燃煤电厂多环芳烃的生成与控制

多环芳烃 (PAHs)对人体健康的危害极大。本文综述了燃煤电厂煤燃烧过程中多环芳烃的生成机理 (直接释放、热解合成和高温缩合机理 )和影响因素 (煤种、温度、锅炉负荷、过剩空气系数、停留时间、钙硫比和一次风 /二次风比 ) ,在此基础上介绍了煤燃烧过程中多环芳烃的各种控制技术和方法     

Sampling and analysis of polycyclic aromatic hydrocarbons (PAH) from two-stroke chain-saw engines

A sampling and analysis method for PAH from two-stroke engines is described. The method, which uses a standard glass fiber filter with a back-up section of Amberlite XAD-2 for sampling and GC or GC-MS for analysis, is suitable for both emission studies and occupational studies during logging. Filters and XAD-2 are desorbed with cyclohexane in an ultrasonic bath. After separation on a silica-gel micro column, the samples are submitted to analyses by capillary GC. The method is simple and covers both gaseous and particulate PAH. Naphthalene and alkyl substituted naphthalenes are also quantified.     

Accumulation of weathered polycyclic aromatic hydrocarbons (PAHs) by plant and earthworm species

Experiments were conducted to assess the bioavailability of polyclycic aromatic hydrocarbons (PAHs) in soil from a Manufactured Gas Plant site. Three plant species were cultivated for four consecutive growing cycles (28 days each) in soil contaminated with 36.3 microg/g total PAH. During the first growth period, Cucurbita pepo ssp. pepo (zucchini) tissues contained significantly greater quantities of PAHs than did Cucumis sativus (cucumber) and Cucurbita pepo ssp. ovifera (squash). During the first growth cycle, zucchini plants accumulated up to 5.47 times more total PAH than did the other plants, including up to three orders of magnitude greater levels of the six ring PAHs. Over growth cycles 2-4, PAH accumulation by zucchini decreased by 85%, whereas the uptake of the contaminants by cucumber and squash remained relatively constant. Over all four growth cycles, the removal of PAHs by zucchini was still twice that of the other species. Two earthworm species accumulated significantly different amounts of PAH from the soil; Eisenia foetida and Lumbricus terrestris contained 0.204 and 0.084 microg/g total PAH, respectively, but neither species accumulated measurable quantities 5 or 6 ring PAHs. Lastly, in abiotic desorption experiments with an aqueous phase of synthetically prepared organic acid solutions, the release of 3 and 4 ring PAHs from soil was unaffected by the treatments but the desorption of 5-6 ring constituents was increased by up to two orders of magnitude. The data show that not only is the accumulation of weathered PAHs species-specific but also that the bioavailability of individual PAH constituents is highly variable.     

The photo-induced toxicity of polycyclic aromatic hydrocarbons to larvae of the fathead minnow (Pimephales promelas)

The toxicity of 12 polycyclic aromatic hydrocarbons to larvae of the fathead minnow in the presence of simulated sunlight was examined. A measure of relative toxicities of the toxic compounds is described in which waveband radiation intensity, molar extinction coefficients, and molar body concentration of PAH are considered. In addition, a structure-lethality relationship has been developed, based on molecular structure and photochemical properties, that classifies compounds as being phototoxic or non-phototoxic.     

Wintertime size distribution of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in the urban environment: Street- vs rooftop-level measurements

The size distribution of ambient air particles and associated organic pollutants, such as polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and organochlorine pesticides (OCPs) including hexachlorocyclohexanes (HCHs), DDT and metabolites, etc., was investigated at a traffic-impacted site of Thessaloniki, Greece. Investigation took place during wintertime of 2006 at two heights above ground: at the street level (1.5 m) and at the rooftop level (15 m). Size-resolved samples (<0.95 μm, 0.95–1.5 μm, 1.5–3 μm, 3–7.5 μm and >7.5 μm) were concurrently collected from the two height levels using five-stage high volume cascade impactors. At both heights, particle mass exhibited bimodal distribution with peaks in the 0.95–1.5 μm and the 3–7.5 μm size fractions, whereas most organic pollutants exhibited one peak at 0.95–1.5 μm. Apart from the 0.95–1.5 μm fraction, particle concentrations of all size ranges were significantly higher at the street level than at the rooftop as a result of more intensive vehicular emissions and road dust resuspension. On the contrary, the concentrations of most organic pollutants did not differentiate significantly between the two elevations.     

Characterization and source identification of polycyclic aromatic hydrocarbons (PAHs) in river bank soils

Elevated PAH concentrations were detected in bank soils along the Mosel and Saar Rivers in Germany. Information on the identification of PAH sources in this area however remains unclear. This study was able to characterize the PAH sources by application of several approaches, including consideration of the distribution patterns of 45 PAHs (including 16 EPA PAHs and some alkyl PAHs), specific PAH ratios, distribution patterns of n-alkanes and principal component analysis (PCA). In addition, the efficiency of the tested approaches was assessed. The results from the application of the various source identification methods showed that pyrogenic PAHs dominate soil samples collected upstream of the confluence of the Mosel and Saar Rivers, and petrogenic and pyrogenic PAHs dominate samples downstream of the confluence. Based on the analysis of reference materials and organic petrography, the petrogenic input was found to be dominated by coal particles. More detailed information on the petrogenic sources was provided by the n-alkane analyses. The current study concludes that to accurately determine the origin of PAHs, several identification methods must be applied.     

Enhancement of nitrogen and phosphorus removal from eutrophic water by economic plant annual ryegrass (Lolium multiflorum) with ion implantation

Severe eutrophication of surface water has been a major problem of increasing environmental concern worldwide. In the present study, economic plant annual ryegrass (Lolium multiflorum) was grown in floating mats as an economic plant-based treatment system to evaluate its potential after ion implantation for removing nutrients in simulated eutrophic water. The specific weight growth rate of L. multiflorum with ion implantation was significantly greater than that of the control, and the peroxidase, nitrate reductase, and acid phosphatase activities of the irradiated L. multiflorum were found to be greater than those plants without ion implantation. Higher total nitrogen (TN) and total phosphorus (TP) removal efficiencies were obtained for the L. multiflorum irradiated with 25 keV 5.2?×?10¹⁶ N⁺ ions/cm² and 30 keV 4.16?×?10¹⁶ N⁺ ions/cm², respectively (p?L. multiflorum itself was directly responsible for 39–49 and 47–58 % of the overall N and P removal in the experiment, respectively. The research results suggested that ion implantation could become a promising approach for increasing phytoremediation efficiency of nutrients from eutrophic water by L. multiflorum.