Uptake and depuration of PAHs and chlorinated pesticides by semi-permeable membrane devices (SPMDs) and green-lipped mussels (Perna viridis)

Semi-batch seawater experiments were conducted to follow the uptake and release of selected PAHs (anthracene, fluorathene, pyrene and B[a]P) and organochlorine pesticides (-HCH, aldrin, dieldrin, p,p′-DDT) in semi-permeable membrane devices (SPMDs) and green-lipped mussels (Perna viridis). Mathematical models were applied to describe the uptake and elimination curves of the contaminants for SPMDs, and kinetic parameters, such as uptake rate constants, and equilibrium triolein/water partitioning coefficients were calculated. SPMD data showed a good fit to estimate rate constant and partition coefficient equations, but only those contaminants which partitioned mainly in the dissolved phase (-HCH and dieldrin) were well explained for mussels. Poor conformity of the other contaminants indicated mussels uptake by routes other than diffusion, such as ingestion of algae. An apparent equilibrium state was only noted for -HCH in mussels. Aldrin was not detected in mussels in the first few days of exposure, indicating potential metabolism of this compound. B[a]P was not detected in the triolein of SPMDs, which suggests that the membrane may act as a reservoir. Loss of spiked B[a]P from the triolein was evident in a depuration experiment, which may indicate transfer to the membrane. Rate constants for mussels were higher than those for SPMDs, but the reverse was true for partition coefficients. Overall, mussels and SPMDs had similar uptake rates for all compounds in this study, excluding p,p′-DDT and dieldrin. Contaminant elimination took place more rapidly in mussels, implying that SPMDs are better candidates for detecting episodic discharge of organic contaminants.     

Effects of some environmental parameters on the reproduction and development of a tropical marine harpacticoid copepod Nitocra affinis f. californica Lang

The effects of salinity, temperature, and light conditions on the reproduction and development of harpacticoid copepod, Nitocra affinis f. californica under controlled laboratory conditions were determined. Seven different salinity levels (5, 10, 15, 20, 25, 30, 35 ppt), four temperatures (20, 25, 30, 35 °C), three different light intensities (25, 56, 130 μmol m⁻² s⁻¹) and photoperiods (24 h:0 h, 1 h:23 h, 12 h:12 h LD cycle) were employed in this study. The highest (p < 0.05) overall reproduction and fastest development time were achieved by copepods reared under 30–35 ppt salinity. The optimum temperature required for the maximum reproduction was 30 °C while under 30 °C and 35 °C the copepod development time was shortest (p < 0.05) compared to other temperature levels. The overall reproduction was highest (p < 0.05) and development rate of N. affinis was shortest (p < 0.05) under lowest light intensity (25 μmol m⁻² s⁻¹). Continuous light (24 h:0 h LD) inhibited the egg production while, continuous darkness (1 h:23 h LD) and 12 h:12 h LD significantly favoured the overall reproductive activity of the female. Photoperiods 1 h:23 h and 12 h:12 h LD yielded highest total (p < 0.05) offspring female⁻¹ coupled with highest (p < 0.05) survival percentage. This study illustrated that although N. affinis can tolerate wide range of environmental conditions, prolonged exposure to subnormal environments affect its reproduction and development. This study showed that this species can be mass cultured for commercial purposes and has a potential to be used for toxicity studies due to its high reproductive performance fast development and a wide range of tolerance to environmental conditions.     

Composition and distribution of organochlorine pesticide residues in surface sediments from the Wu-Shi River Estuary,Taiwan

The contamination of organochlorine pesticides (OCPs) in sediments from the Wu-Shi River estuary was investigated to evaluate the pollution potentials and distribution of OCPs in central Taiwan. A total of 19 sediment samples were collected at five sampling stations along the River estuary. The concentrations of OCPs were in the range of 0.99–14.5 ng/g-dry weight (dw) for ΣHCH (-, β-, γ-, δ-HCH), 0.46–13.4 ng/g-dw for Σcyclodiene and 0.53–11.4 ng/g-dw for ΣDDT (p,p^′-DDD, p,p^′-DDE, p,p^′-DDT). The mean concentrations of ΣHCH, Σcyclodiene and ΣDDT were 3.79, 4.87 and 2.51 ng/g-dw, respectively. The total concentrations of OCPs correspond to 1.73–71.9 μg/g-OC when normalized to TOC contents. Among the organochlorine pesticides, endosulfan sulfate, β-HCH, and p,p^′-DDD were the most dominant compounds in the sediments with the average concentrations of 1.97, 3.43 and 2.08 ng/g, respectively. Also, different contamination patterns among sampling seasons were observed. The measured concentrations of OCPs collected in spring were higher than those in autumn and winter. A linear relationship between sediment characteristics and OCP residues was also demonstrated. The results obtained in this study show that there still exist a variety of organochlorine pesticide residues in the sediments from the near shore of central Taiwan.     

Esterases activities and lipid peroxidation levels in muscle tissue of the shanny Lipophrys pholis along several sites from the Portuguese Coast

This study is part of a project aiming to validate the use of the intertidal shanny Lipophorys pholis as a sentinel species in pollution monitoring in NW European marine ecosystems. To this end, a characterisation of acethylcholin (AChE), butyrylcholin (BChE) and propionylcholin (PrChE) esterases in L. pholis muscle was performed and the results indicated that AChE was predominant. Furthermore, the use of eserine sulphate and BW284c51 (0.64–800 μM), and iso-OMPA (0.08–16 mM), confirmed the measurement of true cholinesterases (ChEs) as well as the presence of pseudocholinesterases. The field application of these markers to L. pholis, sampled in seven locations along the Portuguese coast, revealed that fish were likely to be affected by neurotoxic compounds. This was indicated by the significant depletion of AChE (p < 0.05) in animals collected at urban and industrialised sites, compared with those from reference locations. The inclusion of a marker of effect, measured as lipid peroxidation levels in muscle tissue, also revealed the existence of site differences. Overall, the study further validates the utility of L. pholis in pollution monitoring studies.     

Continuing observation of disturbed reproductive cycle and ovarian spermatogenesis in the giant abalone, Haliotis madaka from an organotin-contaminated site of Japan

Histological examination of gonads as well as chemical analysis of organotin compounds in tissues of the giant abalone, Haliotis madaka, was conducted to evaluate continuing endocrine disruption in abalone populations in Japan. Abalone specimens were collected from two different areas, Tsushima as a reference site and Jogashima as a site representative of declining abalone populations where serious organotin contamination had been observed, each month from January 1998 to March 1999. Scores were given to the development stages of reproductive cells in the ovary and testis. The degree of sexual maturation was evaluated by calculating the mean value of a histogram of these scores for the reproductive cells of each abalone. The temporal variations in degree of sexual maturation showed that female and male abalone from Tsushima matured synchronously, while those from Jogashima did not, which were similar to results of the previous study during September 1995–November 1996. Approximately 19% of the female abalone from Jogashima were masculinized with an ovo-testis, which was also similar to the result of the previous study. The masculinization of female abalone is reported to be induced by tributyltin (TBT) and triphenyltin (TPhT) from antifouling paints. Concentrations of the sum of butyltins (TBT, dibutyltin (DBT) and monobutyltin (MBT): ΣBTs) and the sum of phenyltins (TPhT, diphenyltin (DPhT) and monophenyltin (MPhT): ΣPhTs) in the muscle of abalone from Jogashima (n = 73) of 7.8 ± 9.0 ng/g wet wt. and 4.5 ± 6.8 ng/g wet wt., respectively, were significantly higher than those from Tsushima (n = 87) of 4.7 ± 4.9 ng/g wet wt. and 0.8 ± 1.7 ng/g wet wt., respectively (p < 0.05 for ΣBTs; p < 0.001 for ΣPhTs), although concentrations of TBT and TPhT in the muscle of abalone from Jogashima (n = 73) of 2.2 ± 2.5 ng/g wet wt. and 5.8 ± 5.1 ng/g wet wt., respectively, were insignificantly and significantly higher than those from Tsushima (n = 87) of 0.4 ± 0.6 ng/g wet wt. and 0.5 ± 0.9 ng/g wet wt., respectively, (p > 0.05 for TBT; p < 0.001 for TPhT). Thus, endocrine disruption as well as contamination by organotins in the giant abalone from Jogashima is still persisting.     

Spatial variability and temporal stability of throughfall water under a dominant beech (Fagus sylvatica L.) tree in relationship to canopy cover

Although the spatial heterogeneity of throughfall water (TF) under forest canopies has been related to vegetation structure in several forest types, few reports have been made of the driving factors of small-scale TF variability in deciduous stands. Therefore, the spatial variability of the amount of TF water under one dominant beech (Fagus sylvatica L.) tree was quantified in high temporal and spatial resolution over a 2-year period to examine the temporal stability of spatial TF variability and to relate spatial TF patterns to canopy cover determined photographically above each TF collector (n = 48). The spatial variability of TF was significantly higher during the leafed periods (coefficient of variation (CV) = 18%) than during the leafless periods (CV = 8%), and a strong negative relationship was observed between the CV of event TF and the TF fraction of rainfall in the open field. Geostatistical analysis showed that the cumulative TF water during the leafed periods was spatially correlated up to a distance of 3–4 m. There was a significant temporal stability of spatial TF patterns in the growing periods and in the dormant periods, but patterns differed largely between the two periods of the year. TF water during the growing periods significantly decreased with increasing canopy cover above the sampling locations (r = −0.54, p = 0.014, n = 20), but was more closely correlated with branch cover (r = −0.77, p < 0.001). However, the spatial pattern of TF during defoliated conditions was not related to the measured variation in branch cover.     

Organochlorine pesticide residues in sediments and biota from the coastal area of Dar es Salaam city,Tanzania

Sediment and biota samples were collected from Msimbazi and Kizinga rivers and from the coastal marine environment of Dar es Salaam during both dry and wet seasons. The samples were analyzed for various organochlorine pesticide residues using GC-ECD and GC-MS. Dieldrin, p,p^′-DDT, p,p^′-DDE, p,p^′-DDD, o,p^′-DDT and γ-HCH were detected at significantly greater concentrations above the method detection limits. Recoveries of pesticide residues ranged 86.5–120% in sediments and 62–102% in biota. The average concentrations of total DDT in sediments for the two seasons were almost the same. Biota samples showed significant difference in levels of residues depending on mode of feeding and age of analyzed biota. p,p^′-DDT to total DDT ratios in all matrices indicated recent use of DDT. The levels of residues in sediments suggest possible adverse effects to humans consuming biota that are directly exposed to the sediments. This effect, which is associated with bio-concentration of residues in the tissues of edible aquatic biota, should not affect wildlife. In spite of concern on the adverse effect to humans posed by pesticide residues in sediments, edible biota from the examined water bodies were found to be safe for human consumption.     

Brown mussels (Perna perna) and semi-permeable membrane devices (SPMDs) as indicators of organic pollutants in the South African marine environment

A distinct lack of historical and current data on the status of organic pollutant contaminants within the South African marine environment is evident. This has highlighted the need for more current organic pollutant assessments. Reference mussels and SPMDs were transplanted at five South African harbour sites to assess organic bioaccumulation in brown mussels (Perna perna) and semi-permeable membrane devices (SPMDs). Spatial patterns of PAH and PCB contaminants were determined by GC-MS and GC-ECD after appropriate sample preparation. Significant (p<0.05) spatial differences were observed between the sites. Results indicate no correlations between the passive device and the transplanted mussels; however the SPMDs provided complementary information on the presence of dioxin-like PCBs within the environment not detected by the mussel. The results indicate that information provided by both the mussels and SPMDs allow for a more in depth scrutiny of environmental conditions as a result of anthropogenic influence.     

Field accumulative behavior of organochlorine pesticides. The role of crabs and sediment characteristics in coastal environments

The influence of intertidal crab beds on the concentrations of organochlorine (OC) pesticides in sediment was studied in two different coastal environments in Argentina. Samples of male burrowing crabs (Chasmagnathus granulatus) were collected for this study. Our field data showed lower bioaccumulation of OC pesticides in crabs from sediments with a higher total organic carbon (TOC) and higher clay content. Thus, concentrations in crabs depend on the physico-chemical characteristics of the sediment where they live more than on the OC pesticide concentrations in the environment. The distribution patterns in sediment from inside and outside crab burrows were similar for both coastal areas being HCHs  γ-chlordane > p,p′-DDE for San Antonio Bay (SAO), and HCHs > p,p′-DDE  γ-chlordane for Mar Chiquita (MCh) coastal lagoon. OC pesticide concentrations in sediment were significantly lower inside than outside crab burrows, irrespective of the sediment physico-chemical characteristics due to the bioturbation activity of C. granulatus.     

Levels of organochlorine pesticide residues in some organs of the Ganges perch, Lates calcarifer, from the Ganges-Brahmaputra-Meghna Estuary, Bangladesh

Levels of organochlorine pesticide residues (p,p′ DDT, DDD, DDE, Aldrin, Dieldrin, Lindane, Heptachlor and BHC) were analysed in the dry and wet seasons in four organs (muscle, liver, gut and egg samples) of Ganges Perch, Lates calcarifer, collected during October–November–December, 1996 and May–June–July, 1997 from the Ganges–Brahmaputtra–Meghna estuary. The residues were analysed by using gas-chromatography (GC) in electron capture detector (ECD) mode and were verified by thin layer chromatography (TLC). Among the four organs analysed, the residues were found in the order egg > gut > muscle > liver. The pesticide residues were found in the order ∑DDT > Heptachlor >Dieldrin > Aldrin. Higher levels of residues were found during the dry season due to high lipid content in fishes. A positive correlation was observed between the pesticide residues (∑DDT and ∑OCs) and lipid contents of fish, and the correlation was found to be linear. The concentrations of pesticide residues in muscle, liver and gut were below the FAO/WHO (1993) recommended permissible limit except in eggs.     

Preliminary evaluation of the occurrence of herbicides and PAHs in the Wet Tropics region of the Great Barrier Reef, Australia, using passive samplers

The proximity of the Great Barrier Reef (GBR) Marine Park to areas of intensive agriculture and increasing urbanisation places the park under potential threat of contamination by land-based pollutants. Passive samplers were deployed at inshore reef and river mouth sites in the Wet Tropics region of the GBR during a dry and a wet season to measure levels of land-based organic pollutants in this environment. Two types of passive sampling devices were deployed: (i) a polar sampler, which can be used to monitor polar herbicides and (ii) semipermeable membrane devices (SPMDs) which sequester more hydrophobic compounds (e.g. PAHs, chlorpyrifos). Herbicides (diuron, simazine, atrazine, hexazinone and/or flumeturon) were detected at low concentrations (ng L⁻¹) at all sites sampled and in both seasons. Chlorpyrifos was not detected while PAHs were present in SPMDs at levels below limits of detection. The results show that the GBR environment does contain low levels of organic pollutants and that passive sampling provides a sensitive monitoring tool for measuring waterborne organic pollutants.     

Uptake and depuration of PAHs and chlorinated pesticides by semi-permeable membrane devices (SPMDs) and green-lipped mussels (Perna viridis)

Semi-batch seawater experiments were conducted to follow the uptake and release of selected PAHs (anthracene, fluorathene, pyrene and B[a]P) and organochlorine pesticides (α-HCH, aldrin, dieldrin, p,p′-DDT) in semi-permeable membrane devices (SPMDs) and green-lipped mussels (Perna viridis). Mathematical models were applied to describe the uptake and elimination curves of the contaminants for SPMDs, and kinetic parameters, such as uptake rate constants, and equilibrium triolein/water partitioning coefficients were calculated. SPMD data showed a good fit to estimate rate constant and partition coefficient equations, but only those contaminants which partitioned mainly in the dissolved phase (α-HCH and dieldrin) were well explained for mussels. Poor conformity of the other contaminants indicated mussels uptake by routes other than diffusion, such as ingestion of algae. An apparent equilibrium state was only noted for α-HCH in mussels. Aldrin was not detected in mussels in the first few days of exposure, indicating potential metabolism of this compound. B[a]P was not detected in the triolein of SPMDs, which suggests that the membrane may act as a reservoir. Loss of spiked B[a]P from the triolein was evident in a depuration experiment, which may indicate transfer to the membrane. Rate constants for mussels were higher than those for SPMDs, but the reverse was true for partition coefficients. Overall, mussels and SPMDs had similar uptake rates for all compounds in this study, excluding p,p′-DDT and dieldrin. Contaminant elimination took place more rapidly in mussels, implying that SPMDs are better candidates for detecting episodic discharge of organic contaminants.     

Lysosomal membrane stability and metallothioneins in digestive gland of Mussels (Mytilus galloprovincialis Lam.) as biomarkers in a field study

The lysosomal membrane destabilization and the metallothionein content in the digestive gland cells of mussels (Mytilus galloprovincialis Lam.), collected along the east coast of the North Adriatic (Istrian and Kvarnerine coast, Croatia), were examined over a period of four years (1996–1999). The lysosomal membrane stability, as a biomarker of general stress, showed that the membrane labilization period in mussels from polluted, urban- and industrial-related areas was significantly decreased (p<0.05) when compared to mussels from control, clean sea water sites. In the harbour of Rijeka, the most contaminated site, the lysosomal membrane stability was reduced by more than 70% compared to the control. This method also proved to be a useful biomarker for detection of additional stress caused by short-term hypoxia that occurred once during this study inside the polluted and periodically quite eutrophic Pula Harbour. The concentration of metallothioneins in the mussel digestive gland, as a specific biomarker of exposure to heavy metals, did not reveal significant differences (p<0.05) between sites covered by this study.     

Comparison of mussels and semi-permeable membrane devices as intertidal monitors of polycyclic aromatic hydrocarbons at oil spill sites

Side-by-side comparisons of polycyclic aromatic hydrocarbon (PAH) concentrations in resident blue mussels (Mytilus trossulus) and in semi-permeable membrane devices (SPMDs) were made at four sites in Prince William Sound, Alaska. SPMDs were deployed for approximately 30 days on the surface of the beach sediment at three tidal elevations on each shore and in 0.5 m deep open pits in the middle intertidal zone. Total PAH (TPAH) concentrations in mussels and in SPMDs were correlated, but the PAH compositions were different. The lower molecular weight PAH were relatively more abundant in the SPMDs than in the mussels at oiled and HA sites. TPAH concentrations in SPMDs deployed in pits and mussels collected adjacent to those pits at oiled sites were higher than in SPMDs and mussels from non-pitted SPMD locations approximately 3-15 m from the pits. Pitting released buried oil making its PAH bioavailable. SPMDs deployed in the supratidal zone (+4.0 m tidal elevation) were exposed to atmospheric contaminants for a large fraction of the deployment time and accumulated primarily pyrogenic (combustion-sourced) PAH from the atmosphere. The SPMD strips supplied by the manufacturer contained significant amounts (approximately 125 ng/strip) of primarily alkylated 2-3 ring PAH. These blank levels make SPMDs unsuitable for shoreline assessments when environmental PAH concentrations are low. Consequently, where available, mussels are recommended for use in assessments of the bioavailability of buried oil residues sequestered in intertidal sediments following an oil spill. Mussels are the preferred monitoring tool when the assessments involve food-chain effects. At locations where the absence of mussels necessitates the use of SPMDs or other passive sampling devices, their limitations need to be carefully considered in the interpretation of results.     

A 53 year seasonally resolved oxygen and carbon isotope record from a modern Gibraltar speleothem: Reconstructed drip water and relationship to local precipitation

The response of a climate proxy against measured temperature, rainfall and atmospheric circulation patterns at sub-annual resolution is the ultimate test of proxy fidelity but very few data exist showing the level of correspondence between speleothem climate proxies and the instrumental climate record. Cave sites on the Gibraltar peninsula provide a unique opportunity to calibrate speleothem climate proxies with the longest known available precipitation isotopes and instrumental records. An actively growing speleothem sampled from New St. Michaels Cave in 2004 is composed of paired laminae consisting of light columnar calcite and a darker microsparitic calcite. Stable isotope analysis of samples micromilled in 100 μm steps at the equivalent of bi-monthly intervals reveals fabric-correlated annual cycles in carbon isotopes, oxygen isotopes and trace elements responding to seasonal changes in cave microclimate, hydrology and ventilation patterns. Calcite δ¹³C values reach a minimum in the light columnar fabric and evidence from trace element behaviour and cave monitoring indicates that this grows under cave ‘winter’ conditions of highest pCO₂, whereas the dark microsparitic calcite, characterised by elevated δ¹³C and δ¹⁸O values grows under low ‘summer’ pCO₂ conditions. Drip water δ¹³C_DIC reaches a minimum in March–April, at which time the attenuated δ¹⁸O signal becomes most representative of winter precipitation. An age model based on cycle counting and the position of the ¹⁴C bomb carbon spike yields a precisely dated winter oxygen isotope proxy of cave seepage water for comparison with the GNIP and instrumental climate record for Gibraltar. The δ¹⁸O characteristics of calcite deposited from drip water representing winter precipitation for each year can be derived from the seasonally resolved record and allows reconstruction of the δ¹⁸O drip water representing winter precipitation for each year from 1951–2004. These data show an encouraging level of correspondence (r² = 0.47) with the δ¹⁸O of rainfall falling each year between October and March and on a decadal scale the δ¹⁸O of reconstructed winter drip water mirrors secular change in mean winter temperatures.     

Esterase activities and lipid peroxidation levels in offshore commercial species of the NW Mediterranean Sea

There is a lack of information on monitoring neurotoxicity in offshore commercial species. To help fill this gap, we sampled hake (Merluccius merluccius) and Norway lobster (Nephrops norvegicus) in fishing grounds off the coast of l’Ametlla de Mar (NW Mediterranean) in June 2005 at a depth of 100 m and 400 m. Additionally, at 400 m depth, two other fish species, Micromesistius poutassou and Phycis blennoides were included. Neurotoxicity markers such as Colinesterases (ChEs), namely acethyl- (AChE), butyryl- (BChE), propionyl- (PrChE) and carboxilesterase (CbE) were measured in muscle. Lipid peroxidation (LP), a marker of oxidative damage, was also included. The results are discussed in relation to the animal’s sex, size and fishing depth. A comparison of esterases and LP levels between muscle and liver of hake and between muscle and hepatopancreas of Norway Lobster was made.

AChE was dominant in muscle and CbE in hepatopancreas. No differences between fish species were seen for AChE. However, N. norvegicus, presented lower levels of ChEs and LP. A size-dependence in ChEs was seen for M. merluccius, with larger animals showing significantly lower activities (p < 0.05). Sex-dependence was seen in N. norvegicus for most esterases, except AChE, with males displaying higher activities (p < 0.05). A sampling-depth effect was also seen in the crustacea, with animals from 100 m generally presenting lower esterase activities and higher LP levels.     

Microbial modulation in the biomass and toxin production of a red-tide causing alga

The effect of S₁₀, a strain of marine bacteria isolated from sediment in the Western Xiamen Sea, on the growth and paralytic shellfish poison (PSP) production in the alga Alexandrium tamarense (A. tamarense) was studied under controlled experimental conditions. The results of these experiments have shown that the growth of A. tamarense is obviously inhibited by S₁₀ at high concentrations, however no evident effect on its growth was observed at low concentrations. Its PSP production was also inhibited by S₁₀ at different concentrations, especially at low concentrations. The toxicity of this strain of A. tamarense is about (0.95–12.14) × 10⁻⁶ MU/cell, a peak toxicity value of 12.14 × 10⁻⁶ MU/cell appeared on the 14th day, after which levels decreased gradually. The alga grew well in conditions of pH 6–8 and salinities of 20–34‰. The toxicity of the alga varied markedly at different pH and salinity levels. Toxicity decreased as pH increased, while it increased with salinity and reached a peak value at a salinity of 30‰, after which it declined gradually. S₁₀ at a concentration of 1.02 × 10⁹ cells/ml inhibited growth and the PSP production of A. tamarense at different pH and salinity levels. S₁₀ had the strongest inhibitory function on the growth of A. tamarense under conditions of pH 7 and a salinity of 34‰. The best inhibitory effect on PSP production by A. tamarense was at pH 7, this inhibitory effect on PSP production did not relate to salinity. Interactions between marine bacteria and A. tamarense were also investigated using the flow cytometer technique (FCM) as well as direct microscope counting. S₁₀ was identified as being a member of the genus Bacillus, the difference in 16S rDNA between S₁₀ and Bacillus halmapalus was only 2%. The mechanism involved in the inhibition of growth and PSP production of A. tamarense by this strain of marine bacteria, and the prospect of using it and other marine bacteria in the bio-control of red-tides was discussed.     

Establishing a chronology for lacustrine sediments using a multiple dating approach—A case study from the Frickenhauser See, central Germany

In order to establish a reliable chronology for lacustrine sediments of the Frickenhauser See (central Germany) different dating methods have been applied. A total of 17 AMS ¹⁴C dates, all within the last 2000 years, were supplemented with ¹³⁷Cs/²¹⁰Pb dating and varve counting of the uppermost sediments (131 years). The age–depth model for the Frickenhauser See has to cope with highly variable sedimentation rates and overlapping probability distributions of calibrated ¹⁴C dates. The uncertainty of calibrated ¹⁴C dates could be considerably reduced by including the stratigraphic relationship of the dated samples, the age information derived from short-lived isotopes and varve counting as well as an upper and lower limit of realistic sedimentation rates as ‘a priori’ information in the calibration procedure. Sets of possible age combinations obtained by repeated sampling from the modified probability distributions were used to calculate continuous age–depth relationships based on monotonic smoothing splines. The obtained age–depth model for the sediment record of the Frickenhauser See represents the average of over 16,000 such model runs and suggests a drastic increase in sedimentation rates from around 1–2 mm a⁻¹ (200–1000 AD) to over 25 mm a⁻¹ for the period between 1100 and 1300 AD. From then on, sedimentation rates exhibit relatively stable values around 3–9 mm a⁻¹. ‘Conventional’ age–depth models such as general polynomial regression or cubic splines either do not include the obtained age-information in a satisfying manner (the model being too “stiff”) or exhibit “swings” causing age-reversals in the model. Although the age–depth relationships obtained for monotonic smoothing splines and mixed-effect regression are generally very similar, they differ in their respective sedimentation rates as well as in their uncertainties. Mixed-effect regression resulted in much higher sedimentation rates of more than 37 mm a⁻¹. These results suggest that monotonic smoothing splines give better control of the age–depth model characteristics and are well suited in situations, where the integrity of ¹⁴C dates is high, i.e. the dated material represents the age of the respective layer.     

Imposex in Morula Granulata as Bioindicator of Tributyltin (TBT) Contamination in the Dampier Archipelago, Western Australia

This study was undertaken to examine the use of imposex in the tropical neogastropod whelk Morula granulata as bioindicator of tributyltin (TBT) contamination. Samples were collected from sites throughout the Dampier Archipelago; both impact sites close to intensive shipping activity and remote control sites. TBT in this area originates mainly from commercial vessels using the Port of Dampier that are >25 m in length and exempt from legislation controlling the use of TBT in antifouling paints. A field survey was undertaken in July 1997; 100 M. granulata were taken at each of 18 sites with varying vessel activity, and examined for imposex. The level of TBT contamination in the Archipelago was low; ranging from <0.3 to 25 ng Sn l⁻¹ in water,<0.3 to 80 ng Sn g−¹ in oyster tissue (Saccostrea cuccullata – prey of M. granulata), and <0.3 to 33 ng Sn g⁻¹ in whelks. Percentage of imposex in M. granulata ranged from 0% to 57%, and was correlated with distance to vessel activity (r=0.646, p<0.05). The only significant relationship of imposex with butyltin concentrations was with TBT in oysters (r=0.826, p<0.05), and dibutyltin (DBT) in whelks (r=0.783, p<0.05). It is postulated that this is because of interspecies variation in ability to metabolize TBT to DBT and MBT (monobutyltin), as well as induction of imposex in earlier life stages, so that imposex in adults could be a reflection of prior contamination. M. granulata is a suitable bioindicator of TBT contamination in the Dampier Archipelago, which could be used throughout the Indo-Pacific given its abundance in the region.     

The energetics of aluminum solubility into MgSiO3 perovskite at lower mantle conditions

Experiments [T. Irifune (1994) Nature 370, 131–133; E. Ito et al. (1998) Geophys. Res. Lett. 25, 821–824; A. Kubo, M. Akaogi (2000) Phys. Earth Planet. Int. 121, 85–102] indicate that (Mg,Fe)SiO₃ perovskite, commonly believed to be the most abundant mineral in the Earth, is the preferred host phase of Al₂O₃ in the Earth’s lower mantle. Aiming to better understand the effects of Al₂O₃ on the thermoelastic properties of the lower mantle, we use atomistic models to examine the chemistry and elasticity of solid solutions within the MgSiO₃(perovskite)–Al₂O₃(corundum)–MgO(periclase) mineral assemblage under conditions pertinent to the lower mantle: low Al cation concentrations, P=25–100 GPa, and T=1000–2000 K. We assess the relative stabilities of two likely substitution mechanisms of Al into MgSiO₃ perovskite in terms of reactions involving MgSiO₃, MgO, and Al₂O₃, in a manner similar to the 0 Kelvin calculations of Brodholt [J.P. Brodholt (2000) Nature 407, 620–622] and Yamamoto et al. [T. Yamamoto et al. (2003) Earth Planet. Sci. Lett. 206, 617–625]. We determine the equilibrium composition of the assemblage by examining the chemical potentials of the Al₂O₃ and MgO components in solid solution with MgSiO₃, as functions of concentration. We find that charge coupled substitution dominates at lower mantle pressures and temperatures. Oxygen vacancy-forming substitution accounts for 3–4% of Al substitution at shallow lower mantle conditions, and less than 1% in the deep mantle. For these two pressure regimes, the corresponding adiabatic bulk moduli of aluminous perovskite are 2% and 1% lower than that of pure MgSiO₃ perovskite.