PAHs biodegradation in intertidal surface sediment by indigenous microorganisms

In this study, the 30-day aerobic microorganism-mediated biodegradation of polycyclic aromatic hydrocarbons (PAHs) was investigated in four size fractions (i.e., <0.002, 0.002–0.031, 0.031–0.063 and >0.063 mm) of sand-dominated sediment S1 and mud-dominated S2 collected from intertidal zones in Bohai Bay (China). Prior to biodegradation, the total quantity of phenanthrene, fluoranthene and pyrene comprised more than 80 % of the total quantity of 16 EPA-priority PAHs in each size fraction, with the exception of 70.33 % found in the >0.063 mm fraction of sediment S1. Among the three dominant compounds, the intermediate size fraction (0.031–0.063 mm) showed higher levels of biodegradation than other size fractions in sediment S1 and S2. After pooling data from sediment S1 and S2 for joint analysis, it was observed that the biodegraded portion of the three dominant compounds showed negative correlations with both total organic carbon (TOC) and humic coverage index (HCI) in the size fractions. The observed negative correlation with TOC was in agreement with findings in many other studies, but the negative correlation with HCI had not been observed in early studies, which only investigated aged sediment/soil samples. The findings in this study indicated that the greatest bioavailability of PAHs in intertidal surface sediment may be present in sediment particles of intermediate size and mobility, and that intertidal sediment particles are less likely to experience sufficient ageing given periodical tidal disturbance. These findings have important implications for the assessment of the environmental fate of PAHs in intertidal regions.     

Vertical profile of PCDD/Fs, dioxin-like PCBs, other PCBs, PAHs, chlorobenzenes, DDX, HCHs, organotin compounds and chlorinated ethers in dated sediment/soil cores from flood-plains of the river Elbe, Germany

Concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) and other organic micropollutants were determined in dated sediment/soil cores collected from the flood-plain of the river Elbe near Pevestorf (PT), approximately 125 km upstream of Hamburg, and Heuckenlock (HL) in southeast of Hamburg. Concentrations of PCDD/Fs peaked sharply at PT in the 1950s and at HL at the end of the 1940s. Cluster analyses provide evidence that the region of Bitterfeld-Wolfen (about 350-400 km upstream of Hamburg) could be the source of the PCDD/F contamination existing in the cores PT and HL since the 1940s. Obviously it is caused by sediments of the river Elbe of a similar composition. Whereas the PCDD/Fs, HCHs (hexacyclohexane isomers), DDX (DDT, DDD, DDE), and tetrachlorinated ethers in PT and HL presumably originated predominantly from the Bitterfeld-Wolfen region, organotin compounds in HL and dichlorinated haloethers in HL during the 1940s and 1950s can probably largely be attributed to emissions from the Hamburg region. Although they are separated by a large distance, in both sediment cores PT and HL concentrations and composition patterns of most organic micropollutants analyzed widely match. Inductively it can be concluded that similar contaminations will be found in many of the river bank soils between the Bitterfeld-Wolfen region and Hamburg. Excavation of top soils may uncover highly contaminated materials. Since the dated sediment cores show the variation in contaminants in the Elbe sediments over a defined time period, it is possible to make an approximate assessment of the actual degree of contamination to be expected in areas where in previous decades contaminated dredged sediments from the Elbe and from the Port of Hamburg have been deposited on land and used for building plots or for agricultural purposes.     

Contamination status of dioxins in sediment cores from the Three Gorges Dam area, China

In order to screen dioxin pollution in sediment of Three Gorges Dam (TGD) area, three sediment cores were obtained from two sites in 2010~2011; each core was divided into different samples with every 10 cm depth. Sediment dating determined by radiometry (¹³⁷Cs, ²¹⁰Pb) and concentrations of dioxins were analyzed by high-resolution gas chromatography/mass spectrometry. The results indicated: Sediment dating showed no significant difference among all the samples from the same core and the two locations (ANOVA, p?>?0.05). The total amount of polychlorinated dibenzo-p-dioxins (PCDD)/Fs in all sample ranged from 30.7 to 371 pg/g dry weight (d.w.), with the mean value of 66.2 pg/g d.w. PCDDs occupied 60.33~85.22 % of dioxins in each sample, and PCDFs contributed to a very small extend. There was no significant difference in the dioxin concentration between 2010 and 2011 and in the two locations (t test, p?>?0.05), but the vertical distribution of dioxins showed significant different in different depths. Toxic equivalent (TEQ) (WHO 2005, Humans) of samples ranged from 0.15 to 1.60 pg/g d.w.; the mean was 0.41 pg/g d.w. No significant difference was found in TEQ between 2010 and 2011(t test, p?>?0.05). It could be concluded that the distribution of dioxins showed the spatial heterogeneous which resulted from the strong mixing and sediment deposition characteristics. Dioxin concentration in sediment cores was low with very low environmental risk potential. Dioxins at the two sites had the same origin, and exogenous input was the main source. It is the first report on the dioxins concentrations in sediment cores in the TGD area.     

Contamination of butyltin and phenyltin compounds in the marine environment of Otsuchi Bay, Japan

Butyltin (BT) and phenyltin (PT) compounds were measured in seawater, sediment, and biological samples collected from coastal areas of Otsuchi Bay, Japan. Tributyltin (TBT) compounds in seawater, sediment, plankton, mussels, scallops and fish were in the range of 0.008-0.074 microg liter(-1), 0.01-0.64 mg (kg dry wt)(-1), 0.24-9.8 mg (kg dry wt)(-1), 0.04-0.18 mg (kg wet wt)(-1), 0.10-0.13 mg (kg wet wt)(-1) and 0.01-0.02 mg (kg wet wt)(-1), respectively. Trace amount of PTs were found in seawater. The highest concentrations of TBT and triphenyltin (TPT) were found near a shipyard. Triorganotin compounds were more dominant than their metabolites. A positive correlation was observed between the concentrations of TBT and TPT in the mussels. Concentrations of TBT and TPT in mussels were high in the upper intertidal zone, and decreased toward the water.     

Historical reconstruction of atmospheric lead pollution in central Yunnan province, southwest China: an analysis based on lacustrine sedimentary records

Atmospheric lead (Pb) pollution during the last century in central Yunnan province, one of the largest non-ferrous metal production centers in China, was reconstructed using sediment cores collected from Fuxian and Qingshui Lakes. Lead concentrations and isotopic ratios (²⁰⁷Pb/²⁰⁶Pb and ²⁰⁸Pb/²⁰⁶Pb) were measured in sediment cores from both lakes. The operationally defined chemical fractions of Pb in sediment core from Fuxian Lake were determined by the optimized BCR procedure. The chronology of the cores was reconstructed using ²¹⁰Pb and ¹³⁷Cs dating methods. Similar three-phase variations in isotopic ratios and enrichment factors of Pb were observed in the sediment cores from both lakes. Before the 1950s, the sediment data showed low ²⁰⁷Pb/²⁰⁶Pb and ²⁰⁸Pb/²⁰⁶Pb ratios and enrichment factors (EFs?=?~1), indicating that the sedimentary Pb was predominantly of lithogenic origin. However, these indices were increased gradually between the 1950s and the mid-1980s, implying an atmospheric Pb deposition. The EFs and isotopic ratios of Pb reached their peak during recent years, indicating aggravating atmospheric Pb pollution. The average anthropogenic Pb fluxes since the mid-1980s were estimated to be 0.032 and 0.053 g m^?2 year^?1 recorded in Fuxian and Qingshui cores, respectively. The anthropogenic Pb was primarily concentrated in the reducible fraction. Combining the results of Pb isotopic compositions and chemical speciations in the sediment cores and in potential sources, we deduced that recent aggravating atmospheric Pb pollution in central Yunnan province should primarily be attributed to regional emissions from non-ferrous metal production industries.     

Concentrations of organotin compounds in sediment and clams collected from coastal areas in Vietnam

Levels of butyltin (BT) and phenyltin (PT) compounds were determined in sediments and clam Meretrix spp. collected from north and central coastal areas in Vietnam. Concentrations of TBT in sediments ranged from 0.89 to 34 ng g(-1) dry wt and those in clams ranged from 1.4 to 56 ng g(-1) wet wt. The levels of TBT in sediments and clams from Vietnam were within limits reported from other countries. Further, the TBT level in clams was lower than the tolerable average residue level (TARL) estimated based on tolerable daily intake (TDI). Trace amounts of PTs were also found in both sediment and clam samples. In sediments from north and central Vietnam, the concentrations of TBT were highest in the order of Hue (28 ng g(-1) dry wt), Cua Luc (15 ng g(-1) dry wt), Sam Son (6.3 ng g(-1) dry wt), and Tra Co (5.5 ng g(-1) dry wt). Among the clams from north and central Vietnam, the levels of TBT in clams from Cua Luc were dramatically high at 47 ng g(-1) wet wt. TBT formed the principal butyltin species in sediment at all sites studied. The ratios of TBT in sediment were higher among BT compounds at all study sites. Of total BTs, TBT was the dominant species in clams from almost all sites studied. In spatial distribution, TPT showed a pattern similar to TBT, suggesting the use of TPT as an antifouling paint. The partition coefficient between sediment and calms was calculated. The partition coefficients of TBT and TPT were 2.01 (0.56-5.5) and 9.23 (3.1-20), respectively. These results show that sediment-bound TBT is a source of contamination to clams in addition to dissolved TBT.     

Characterization of dioxin-like contamination in soil and sediments from the ��hot spot�� area of petrochemical plant in Pancevo (Serbia)

Purpose

Combinatorial bio/chemical approach was applied to investigate dioxin-like contamination of soil and sediment at the petrochemical and organochlorine plant in Pancevo, Serbia, after the destruction of manufacturing facilities that occurred in the spring of 1999 and subsequent remediation actions.

Materials and methods

Soil samples were analyzed for indicator polychlorinated biphenyls (PCBs) by gas chromatography/electron capture detection (GC/ECD). Prioritized soil sample and sediment samples from the waste water channel were analyzed for polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) by high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS). Microethoxyresorufin o-deethylase (Micro-EROD) and H4IIE?Cluciferase bioassays were used for monitoring of dioxin-like compounds (DLC) and for better characterization of dioxin-like activity of soil samples.

Results

Bioanalytical results indicated high dioxin-like activity in one localized soil sample, while the chemical analysis confirmed the presence of large quantities of DLC: 3.0?×?10⁵ ng/g d.w. of seven-key PCBs, 8.2 ng/g d.w. of PCDD/Fs, and 3.0?×?10⁵ ng/g d.w. of planar and mono-ortho PCBs. In the sediment, contaminant concentrations were in the range 2?C8 ng/g d.w. of PCDD/Fs and 9?C20 ng/g d.w. of PCBs.

Conclusions

This study demonstrates the utility of combined application of bioassays and instrumental analysis, especially for developing and transition country which do not have capacity of the expensive instrumental analysis. The results indicate the high contamination of soil in the area of petrochemical plant, and PCDD/Fs contamination of the sediment from the waste water channel originating from the ethylene dichloride production.     

Evaluation of geochemical methods for discrimination of metal contamination in Antarctic marine sediments: a case study from Casey Station

Detecting anthropogenic metal contamination in regional surveys can be particularly difficult when there is a lack of pre-disturbance data, especially when trying to differentiate low to moderate levels of contamination from background values. Furthermore, comparisons with other regional studies are confounded by differing analytical methods used and variations in sediment properties such as grainsize. Several types of geochemical technique, including weak acid partial extraction, strong acid extractions and total digestion have been used. Attempts have been made to overcome the influence that grainsize has on chemical concentrations in heterogeneous environments by analysing the fines, typically the mud fraction (<63 microm), in an attempt to improve the detection of anthropogenic contamination. Here we compare a weak acid partial extraction using 1M HCl and total digestion methods for a regional survey of reference and impacted sites in Antarctica using both whole sediment (<2 mm) and mud (<63 microm) fractions. The 1M partial extraction on whole sediment (<2 mm) most closely distinguished weakly, or moderately, impacted sites from reference locations. It also identified small scale within-location spatial variation in metal contamination that the total digest did not detect. Compared with total digests or analysis of the <63 microm fraction alone, this method minimised the possibility of a Type II statistical error in the regional survey - that is, failing to identify a site as being contaminated when it has elevated metal concentrations. To allow inter-regional comparison of sediment chemistry data from elsewhere in Antarctica, and also more generally, we recommend a 1M HCl partial extraction on whole sediment (<2 mm).     

Records of polychlorinated biphenyls (PCBs) in sediments of four remote Chilean Andean Lakes

Sediment cores from four Chilean lakes along the Andes Chain (Chungará, Laja, Castor and Venus) were analysed in order to investigate PCB concentrations and distributions in sediment samples. Sediment cores were analysed for PCBs using gas chromatography (GC-ECD/MS) and radioisotopically dated using 210Pb. Organic carbon content (OC) and 210Pb fluxes were also measured. Results showed that sediment PCB concentrations (ngg(-1) d.w.) at Lake Chungará (1.2 +/- 1) in northern Chile, Laja (5 +/- 4) in central, and in Lake Castor (3.5 +/- 4) in southern Chile (the eastern side of the Andes Mountain) were lower than sediments collected from Lake Venus (64 +/- 30) located in southern Chile (the western side) which contained 15-fold higher concentrations of PCBs. The percentage (%) of organic carbon was variable and showed a high range of values in the sediment fluctuating from 2% (Lake Laja) to 22% (Lake Chungará). Analysis of 210Pb fluxes, presented a decrease trend following Lake Laja>Castor>Chungará with a positive correlation with rainfall at each site. Sedimentation rates in Lake Castor (1846 gm(-2)yr(-1)) were higher than at Chungará (748 gm(-2)yr(-1)) and Lake Laja (508 gm(-2)yr(-1)). Focusing factor (FF) is used as a tool to elucidate PCB input in the aquatic ecosystem. FF were lower (<1) for the shallower lakes (Lakes Chungará and Castor). This study provides background levels of PCBs at remote lakes in Chile. Differences in geographical characteristics (orographic effect) might play an important role in the arrival of PCBs, particularly into the southern lakes. PCB fluxes indicated deposition of PCBs in recent sediments is higher than in previous years with peaks of PCB between 1991 and 1998. The continuing increase of PCB inputs in remote Chilean lakes, could be associated with long range atmospheric transport (LRAT).     

Lead contamination and source in Shanghai in the past century using dated sediment cores from urban park lakes

Lead contamination becomes of importance to urban resident health worldwide, especially for child health and growth. Undisturbed lake sediment cores are increasingly employed as a useful tool to backdate environmental contamination history. Five intact sediment cores collected from lakes in five urban parks were dated using (210)Pb and analyzed for total Pb content and isotope ratio to reconstruct the Pb contamination history over the last century in Shanghai, China. Total Pb content in the sediment cores increased by about 2- to 3-fold since 1900s. The profile of Pb flux in each sediment core revealed a remarkable increase of Pb contamination in Shanghai over the past century, especially in the latest three decades when China was experiencing a rapid economic and industrial development. Significant correlations were found between Pb fluxes in sediment cores and Pb emission from coal combustion in Shanghai. Coal combustion emission dominated anthropogenic Pb sources during the past century contributing from 52% to 69% of total Pb in cores, estimated by a three-end member model of Pb isotope ratios. Leaded gasoline emission generally contributed <30% of total Pb, which was banned by 1997 in the Shanghai region. Our results implicate that coal combustion-based energy consumption should be replaced, or at least partially replaced, to reduce health risks of Pb contamination in Shanghai.     

Distribution of organotin compounds in tissues of mussels Mytilus edulis and clams Mya arenaria

Concentrations and composition of butyltin (BT) and phenyltin (PT) compounds were compared in tissues of mussels Mytilus edulis and clams Mya arenaria collected from the Mersey Estuary. Tributyltin (TBT) concentrations were consistently highest in digestive gland and low in muscular tissues such as siphons (Mya) and adductor muscle (Mytilus). Lowest concentrations were found in the periostracum surrounding the siphons of Mya. Ratios of monobutyltin (MBT), dibutyltin (DBT) and TBT to total BT content of Mytilus tissues were in the ranges 25-34%, 21-28% and 44-51%, respectively. Much higher proportions of TBT:total BT were characteristic of Mya (>80% in the digestive gland, remaining tissue and gonad) implying that slow degradation rates account for the relatively high levels of TBT in this species. TPT was the only phenyltin compound detected (albeit at relatively low levels), and, like TBT, was present in highest concentrations in the digestive gland of clams--suggesting an important dietary component in the accumulation of OTs in these bivalves.     

Distributions, sources, and ecological risks of hexachlorocyclohexanes in the sediments from Haihe Plain, Northern China

The levels of hexachlorocyclohexanes (HCHs) in the sediments from Haihe Plain, China, were measured by a gas chromatograph with a ⁶³Ni microelectron capture detector. The spatial distributions, possible sources, and potential ecological risks of these compounds were analyzed. The residual level of total HCHs was 33.84?±?173.37 ng?g^?1 dry weight (d.w.) with ranges of 0.13?～?1,107.41 ng?g^?1 d.w. Much higher ΣHCH contents were found in the lower reaches of some rivers and in the mouth of the main stream receiving tributaries. The predominance of β-HCH (36 %) in the sediments was similar to that in the soils from Haihe Plain. The high percentages of γ-HCH (23–41 %) could be detected at 25 % of the sampling sites in the seven river systems. There were statistically significant positive relationships between the contents of HCHs and total organic carbon. Lindane was identified as the primary source of HCHs in the sediments, and it seemed that recent illegal lindane inputs still existed in some areas in Haihe Plain, as indicated by the α-/γ-HCH and β-/(α?+?γ)-HCH ratios. Severe potential ecological risks of γ-HCH to benthic organisms at some sampling sites were found based on the consensus-based sediment quality guidelines.     

Particle-size-fractioned transfer of dioxins from sediments to water columns by resuspension process

Particle-size-fractioned transfer of dioxins from sediments to water columns by resuspension process was investigated, using supernatant samples obtained from shaking experiments of sediment-water pairs simulating natural disturbances. The concentrations (dry-matter mass basis) of individual compounds (Cfraction) in two particle size fractions (0.1-1 and 1-10 μm) in the supernatants were generally slightly higher than those in the original sediment (Csed). Cfraction/Csed ratios ranged from 0.45 to 5.9 (median 1.5) without consistent differences among congener groups or consistent correlations against the number of chlorine atoms. The dioxin concentrations in the water column associated with the remaining sediment particles can therefore be estimated by those in the original sediment and by the concentration of suspended sediment particles in the water. The concentration of each compound in the remaining sediment particles (mostly 0.1-10 μm in size) can be roughly estimated by multiplying the concentration in the original sediment by 1.5.     

Kinetic analysis of constructed systems for the recovery of contaminated areas by acid mine drainage

INTRODUCTION: Flowing of the acid mine drainage may contaminate the adjacent water bodies causing substantial changes in the aquatic ecosystem. This aspect is the most relevant problem in the southern of Santa Catarina once the contaminated areas are inserted in the watershed of the Araranguá, Urussanga, and Tubar?o rivers, increasing the need for recovery studies. These areas are between Criciúma, I?ara, Urussanga, Siderópolis, Lauro Müller, Orleans, and Alfredo Wagner towns where a conservation unit exist called the Environmental Preservation Area of Baleia Franca. Aiming to compare the kinetics of the ash derived from burning coal and to neutralize acid mine drainage, different neutralizer, limestone, fly, and bottom ash, was mounted on a pilot scale experiment. DISCUSSION: The transport parameters showed the same order of infiltration and dispersion: fly ash < bottom ash < limestone. The order of measured alkalinity was: limestone < fly ash < bottom ash, with pH values of 9.34, 12.07, and 12.25, respectively. The limestone kinetics of acidic drainage neutralization was first order with reaction rate constant k?=?0.0963 min(-1), bottom ash was 3/4 with k?=?0.0723 mol(1/4) L(-1/4) min(-1), and the fly ash had higher order kinetics, 4/3, with reaction rate constant k?=?27.122 L(1/3) mol(-1/3) min(-1). However, by mathematical modeling, it was found that due to a combination of transport and kinetics, only limestone treatment reached a pH above 6 within 5 years, corresponding to the ideal as planned.     

Surface-sediment and hermit-crab contamination by butyltins in southeastern Atlantic estuaries after ban of TBT-based antifouling paints

Butyltin (BT) contamination was evaluated in hermit crabs from 25 estuaries and in sediments from 13 of these estuaries along about 2,000 km of the Brazilian coast. BT contamination in hermit crabs ranged from 2.22 to 1,746 ng Sn g^-1 of DBT and 1.32 to 318 ng Sn g^-1 of TBT. In sediment samples, the concentration also varied widely, from 25 to 1,304 ng Sn g^-1 of MBT, from 7 to 158 ng Sn g^-1 of DBT, and from 8 to 565 ng Sn g^-1 of TBT. BTs are still being found in surface sediments and biota of the estuaries after the international and Brazilian bans, showing heterogeneous distribution among and within estuaries. Although hermit crabs were previously tested as an indicator of recent BT contamination, the results indicate the presence of contamination, probably from resuspension of BTs from deeper water of the estuary.

Heavy metal deposition and variation in sedimentation rate within a sedimentary basin in Central Gulf of Finland

In studies dealing with the chemical distribution of elements in marine soft sediments, variations in sedimentation rate within a basin can bias the interpretation of the data. A basin in the central part of the Gulf of Finland was sampled at nine sampling sites along a transect, 1.2 nautical miles long. Gravity cores of the topmost recent sediment were analysed for nitric acid leachable concentrations of heavy metals. Almost without exceptions the metal concentrations were lower in the surface sediment, indicating a decrease in pollution load during the last decade. The sedimentation rates within the basin differed substantially, from 2.5 mm a-1 to some 15 mm a-1. Without dating of the sediments, the comparison of different cores is almost impossible. Dating is essential, as is thorough investigation of the basins used in sediment monitoring.     

Responses of kinetics and capacity of phenanthrene sorption on sediments to soil organic matter releasing

Soil organic matter (SOM) releasing with dissolved organic matter (DOM) formed in solution was confirmed in a sediment/water system, and the effects of SOM releasing on the sorption of phenanthrene on sediments were investigated. Inorganic salt (0–0.1 mol L^?1 NaCl) was used to adjust SOM releasing, and two sediments were prepared, the raw sediment (S1) from Weihe River, Shann’xi, China, and the eluted sediments with and without DOM supernatant remained, termed as S2a and S2b, respectively. The FTIR and ¹H NMR analysis indicate that the low molecular weight hydrophilic SOM fraction released prior to the high molecular weight hydrophobic fraction. As a response, phenanthrene sorption kinetics on S1 showed atypical and expressed as three stages: rapid sorption, pseudo sorption with partial desorption, and slow sorption, thus a defined “sorption valley” occurred in kinetic curve. In all cases, partition dominates the sorption, and sorption capacity (K_d) ranked as S2b > S1 > S2a. Compared with the alterations of sediment characters, DOM solubilization produced by SOM releasing exhibited a greater inhibitory effect on sorption with a relative contribution of 0.67. Distribution coefficients (K_doc) of PHE into DOM clusters were 2.10?×?10⁴–4.18?×?10⁴ L kg^?1, however a threshold concentration of 6.83 mg L^?1 existed in DOM solubilization. The study results will help to clarify PAHs transport and their biological fate in a sediment/water system.     

Occurrence of butyltin residues in sediment and mussel tissues from the lower-most Tennessee River and Kentucky Lake, U.S.A

Surface sediments and mussel samples were collected at six selected locations in the lower-most Tennessee River and Kentucky Lake, U.S.A. and analyzed for butyltin (BT) derivatives. In sediments, total BT concentrations ranged from 6.8 to 356 ng g-1 dry wt. A wide range of concentrations in sediments suggested the presence of localized area of contamination. In mussel tissues, total BT concentrations varied between 26-107 ng g-1 dry wt. BT levels were comparable to the levels reported in mussels from some coastal sites as well as a few freshwater ecosystems. Leaching of tributyltin-containing anti-fouling paints in the ocean-going ships is a source of tributyltin, and discharge of municipal sewage and industrial waste waters in to this watershed may account for the presence of the monobutyltin and dibutyltin derivatives detected in the samples. To our knowledge, this is the first report on the butyltin concentrations in sediment and mussel tissues from the lower-most Tennessee River and Kentucky Lake.     

Distribution of lead, copper and zinc in size-fractionated river bed sediment in two agricultural catchments of southern Ontario, Canada

Metal (Pb, Cu and Zn) partitioning in six separated sediment size fractions (<8, 8-12, 12-19, 19-31, 31-42, 42-60 microm) of river bed sediment have been analyzed by sequential extraction. The concentrations of some major elements (Si, Al, Ca, Mg, K, Na, Fe, Mn and P), and organic and inorganic C were determined to correlate the elemental composition of the sediment with metal speciation and grain size. Results show that Zn and Pb concentrations increase with decreasing grain size. For Big Creek and Big Otter Creek, respectively, the highest concentrations of Zn (326 and 230 mg kg(-1)) and Pb (158 and 67 mg kg(-1)) were found in the smallest (<8 microm) fraction, whereas the Cu levels (619 and 1281 mg kg(-1)) were most abundant in the second smallest (8-12 microm) fraction. The major accumulative phases for Cu, Zn and Pb were carbonates, Fe/Mn oxides and organic matter, but the relative importance of each phase varied for individual metals and grain sizes. The extraction data show increasing potential bioavailability of metals with decreasing grain size. Estimates of metal yields in the study catchments suggest that over 80% of the metal yield in sediment smaller than 63 microm is associated with solids smaller than 31 microm.     

Release of fluorocarbons from insulation foam in home appliances during shredding

It is a current practice that refrigerators and freezers in many countries are shredded after the end of useful lives. The shredder residue is deposited in landfills. During the shredding process a significant fraction of blowing agent (BA) in the insulation foam may be released into the atmosphere. The objective of this study is to determine the fraction of BA released from foam during shredding, by comparing the BA content in insulation foam of refrigerator units before shredding with the BA content of shredded foam. All foam samples analyzed were manufactured with trichlorofluoromethane [CFC-11 (CCl3F)] as BA. The average content of BA in the insulation foam from eight U.S. refrigerator units manufactured before 1993 was found to be 14.9% +/- 3.3% w/w. Several refrigerator units also identified as being manufactured before 1993 were stockpiled and shredded at three shredder facilities, of which one was operated in both wet and dry modes. The selected shredder facilities represent typical American facilities for shredding automobiles, refrigerators, freezers, and other iron containing waste products. Shredded material was collected and separated on location into four particle size categories: more than 32 mm, 16-32 mm, 8-16 mm, and 0-8 mm. Adjusting for sample purity, it was found that the majority (>81%) of the foam mass was shredded into particles larger than 16 mm. The smallest size fraction of foam (0-8 mm) was found to contain significantly less BA than the larger size categories, showing that up to 68% +/- 4% of the BA is released from these fine particles during the shredding process. Because only a minor fraction of the foam is shredded into particles smaller than 8 mm, this has a minor impact on the end result when calculating the total BA release from the shredding process. Comparing BA content in shredded samples from the three shredder facilities with the measured average BA content of the eight refrigerator units, it was found that on average 24.2% +/- 7.5% of the initial BA content is released during the shredding process.