Jochen F. Müller

Pesticide and Herbicide Residues in Sediments and Seagrasses from the Great Barrier Reef World Heritage Area and Queensland Coast

Pesticides and herbicides including organochlorine compounds have had extensive current and past application by Queenslands intensive coastal agriculture industry as web as for a wide range of domestic, public health and agricultural purposes in urban areas, The persistent nature of these types of compounds together with possible continued illegal use of banned organochlorine compounds raises the potential for continued long-term chronic exposure to plants and animals of the Great Barrier Reef. Sediment and seagrass samples were collected from 16 intertidal and 25 subtidal sampling sites between Torres Strait and Townsville, near Mackay and Gladstone, and in Hervey and Moreton Bays in 1997 and 1998 and analysed for pesticide and herbicide residues. Low levels of atrazine (0.1-0.3 mug kg(-1)), diuron (0.2-10.1 mug kg(-1)), lindane (0.08-0.19 mug kg(-1)), dieldrin (0.05-0.37 mug kg(-1)), DDT (0.05-0.26 mug kg(-1)), and DDE (0.05-0.26 mug kg(-1)) were detected in sediments and/or seagrasses. Contaminants were mainly detected in samples collected along the high rainfall, tropical coast between Townsville and Port Douglas and in Moreton Bay. Of the contaminants detected, the herbicide diuron is of most concern as the concentrations detected have some potential to impact local seagrass communities, (C) 2000 Elsevier Science Ltd. All rights reserved.

New type of dual-channel PAM chlorophyll fluorometer for highly sensitive water toxicity biotests

A new type of dual-channel PAM chlorophyll fluorometer has been developed, which is specialised in the detection of extremely small differences in photosynthetic activity in algae or thylakoids suspensions. In conjunction with standardised algae cultures or isolated thylakoids, the new device provides an ultrasensitive biotest system for detection of toxic substances in water samples. In this report, major features of the new device are outlined and examples of its performance are presented using suspensions of Phaeodactylum tricornutum (diatoms) and of freeze-dried thylakoids of Lactuca sativa (salad). Investigated and reference samples are exposed to the same actinic intensity of pulse-modulated measuring light. The quantum yields are assessed by the saturation pulse method. Clock-triggered repetitive measurements of quantum yield typically display a standard deviation of 0.1%, corresponding to the inhibition induced by 0.02 μg diuron l−1. Hence, for diuron or compounds with similar toxicity, the detection limit is well below the 0.1 μg l−1 defined as the limit for the presence of a single toxic substance in water by the European Commission drinking water regulation. The amounts of water and biotest material required for analysis are very small, as a single assay involves two 1 ml samples, each containing ca. 0.5 μg chlorophyll. Both with Phaeodactylum and thylakoids the relationship between inhibition and diuron concentration is strictly linear up to 10% inhibition, with very similar slopes. Apparent inhibition depends on the actinic effect of the measuring light, showing optima at 6 and 4 μmol quanta m−2 s−1 with Phaeodactylum and thylakoids, respectively.

Pesticides in Sediments From Queensland Irrigation Channels and Drains

Abstract Pesticide concentration in sediment from irrigation areas can provide information required to assess exposure and fate of these chemicals in freshwater ecosystems and their likely impacts to the marine environment. In this study, 103 sediment samples collected from irrigation channels and drains in 11 agricultural areas of Queensland were analysed for a series of past and presently used pesticides including various organochlorines, synthetic pyrethroids, benzoyl ureas, triazines and organophosphates. The most often detected compounds were endosulphans (α, β and/or endosulphan sulphate) which were detectable in 78 of the 103 samples and levels ranged from below the limit of quantification (0.1 ng g−1 dw) up to 840 ng g−1 dw. DDT and its metabolites were the second most often detected pesticide investigated (74 of the 103 samples) with concentrations up to 240 ng g−1 dw of ∑DDTs. Mean ∑endosulphan and ∑DDT concentrations were 1–2 orders of magnitude higher in sediments from the irrigation areas which are dominated by cotton cultivation compared to those which are dominated by sugarcane cultivation. In contrast to these insecticides, the herbicides diuron, atrazine and ametryn were the compounds which were most often detected in sediments from irrigation drains in sugarcane areas with maximum concentrations in areas of 120, 70 and 130 ng g−1 dw, respectively. In particular during flood events, when light is limiting, transport of these photosynthesis inhibiting herbicides from the sugarcane cultivation areas to the marine environment may result in additional stress of marine plants.

Evidence for the presence of a widespread PCDD source in coastal sediments and soils from Queensland, Australia

Recent studies have demonstrated the occurrence of elevated levels of higher chlorinated PCDDs in the coastal environment of Queensland, Australia. This study presents new data for OCDD contamination and full PCDD/F profile analysis in the environment of Queensland. Marine sediments, irrigation drain sediments and topsoil were collected from sites that were expected to be influenced by specific land-use types. High OCDD concentrations were associated mainly with sediments collected near the mouth of rivers which drain into large catchments in the tropical and subtropical regions. Further, analysis of sediments from irrigation drains could be clearly differentiated on the basis of OCDD contamination, with high concentrations in samples from sugarcane drains collected from coastal regions, and low concentrations in drain sediments from drier inland cotton growing areas. PCDD/F congener-specific analysis demonstrated almost identical congener profiles in all samples collected along the coastline. This indicates the source to be widespread. Profiles were dominated by higher chlorinated PCDDs, in particular OCDD whereas 2,3,7,8-substituted PCDFs were below the limit of quantification in the majority of samples. The full PCDD/F profile analysis of samples strongly resemble those reported for lake sediments from Mississippi and kaolinite samples from Germany. Strong similarities to these samples with respect to congener profiles and isomer patterns may indicate the presence of a similar source and/or formation process that is yet unidentified.

Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans in sediments from Hong Kong

Concentrations of 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were determined in 14 sediment samples collected from four sites in the Mai Po Marshes Nature Reserve (within a RAMSAR Site) and from another six sites in Victoria Harbour and along the Hong Kong coastline. Elevated levels of PCDDs, and particularly OCDD, were detectable in all samples collected from the Mai Po Marshes and five of the six sites. In contrast to PCDDs, PCDFs were mainly found in sediment samples collected from industrial areas (Kwun Tong and To Kwa Wan) in Victoria Harbour. PCDD/ F levels and congener profiles in the samples from the Mai Po Marshes Nature Reserve in particular show strong similarities to those reported in studies which have attributed similar elevated PCDD concentrations to nonanthropogenic PCDD sources.

PAHs, PCDD/Fs, PCBs and HCB in leaves from Brisbane, Australia

The concentrations of SOCs in leaves of an evergreen Australian native tree (Melaleuca leucadendra) and grass collected in Brisbane, Australia were determined. The concentrations of PCDD/Fs and PAHs in the leaf tissue were comparable to those reported for urbanised areas in other industrialised countries. A distinct difference in the compound profiles between the leaves of the two species was observed, with higher concentrations of the lower molecular mass PAHs and PCDD/Fs and lower concentrations of the higher molecular mass PAHs and PCDD/Fs in the Melaleuca leaves relative to the grass leaves. The interspecies differences are explained on the basis of the larger size of the lipophilic compartment (for compounds with low K(OA)) and the lower ratio of surface area to volume in the Melaleuca leaves.

PCDDs, PCDFs, PCBs and HCB in marine and estuarine sediments from Queensland, Australia

Concentrations of 2,3,7,8-chlorine substituted PCDDs, PCDFs, selected PCB congeners and HCB were determined in sediment samples collected from sites along the east coast of Queensland in northern Australia. PCDDs were detectable in all sediment samples while PCDFs, PCBs and HCB were mainly found in sediment samples collected from sites in the Brisbane metropolitan area. The results provide evidence that an unidentified source for higher chlorinated PCDDs exists along the Queensland coast.

Trace organic compounds in the marine environment

Trace organic chemicals include a range of compounds which, due to a combination of their physico-chemical properties and toxicological implications, have been described as a serious threat to the biotic environment. A global treaty to regulate the manufacture and release of some of the most persistent trace chemicals has been promulgated and signed. The marine environment is an important sink for many trace chemicals, some of which accumulate in the marine food chain and in particular in marine mammals. With respect to the global distribution of trace organic chemicals, the levels of organohalogen compounds in the Southern Hemisphere are comparatively lower for a given environmental compartment and latitude compared to the Northern Hemisphere. A debate is currently evolving about the toxicity of alternative halogen substitutions such as bromine instead of chlorine and also of mixed halogen substitution. Recently a series of potentially natural bioaccumulative and persistent organohalogen chemicals have been found in marine mammals and turtles at levels in excess of those of anthropogenic trace organochlorines including PCBs and DDE. Little is known about the sources, behaviour and effects of natural trace organic chemicals. This manuscript presents an overview on the occurrence of trace organic chemicals in different compartments of the aquatic environment. Important knowledge gaps with regards to trace chemicals in the marine environment are presented.

Passive sampling of atmospheric SOCs using tristearin-coated fibreglass sheets

Tristearin-coated fibreglass sheets were evaluated as passive samplers for semivolatile organic chemicals in ambient atmosphere. Kinetic and equilibrium experiments were set-up to independently determine model parameters. The results demonstrate that the tristearin/air partition coefficients (KSV) can be related to the octanol/air partition coefficients (KOA). Furthermore, a linear relationship between the time constant of the clearance kinetics and KSV suggests that uptake of gaseous polycyclic aromatic hydrocarbons (PAHs) in the sampler was controlled by the air side resistance. A field evaluation of the predictive ability of the sampler was set-up at sites in Brisbane, Australia and Bayreuth, Germany. The results demonstrated that this novel sampler provides a reproducible means to collect gaseous PAHs in the environment. Furthermore, the results of the field evaluation in Brisbane are in good agreement with air samples collected with a filter/adsorbent high-volume air sampler at the same sites. In contrast the predicted results obtained from the field evaluation near Bayreuth were less satisfactory. This might be due to sampling artifacts which occurred with the passive samplers, caused by PAH burdened particles eroded from adjacent needles and leaves.

Investigations into the PCDD contamination of topsoil, river sediments and kaolinite clay in Queensland, Australia

Recent findings of elevated PCDDs from an unknown source in the coastal marine environment of Queensland, Australia has instigated further investigations into the distribution of, and environments associated with the PCDD contamination. This study presents data for OCDD concentrations in the coastal, mountainous and inland environment of Queensland. Additionally, full 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins and dibenzofuran (PCDD/F) profiles from different land-use types and environments in the coastal region were analysed. Distinct east-west gradients were detected in topsoil collected from various bushland regions with elevated OCDD concentrations confined to the coastal region. However, PCDD/F results from topsoil and river sediments collected in the Queensland coastal region suggest that elevated OCDD concentrations cannot be attributed to any of the environments, land-use or industry types investigated. PCDD/F congener profiles from select samples were remarkably similar to those previously described in marine sediments collected along the entire Queensland coastline. In addition, kaolinite clay samples from Queensland exhibited elevated OCDD concentrations, and PCDD/F profiles in these samples were similar to those detected in kaolinite clays elsewhere. Natural formation processes have been hypothesised as the source of elevated PCDDs in Queensland and other locations, where similar PCDD/F profiles and the general lack of anthropogenic sources are evident. This study presents additional data supporting this hypothesis and provides further information that may assist in the identification of the processes involved in the natural formation of PCDDs.