Evaluation of food chain transfer of the antibiotic oxytetracycline and human risk assessment

There has been recent concern regarding the possibility of antibiotics entering the aquatic food chain and impacting human consumers. This work reports experimental results of the bioconcentration of the antibiotic oxytetracycline (OTC) by the Asian watermeal plant (Wolffia globosa Hartog & Plas) and bioaccumulation of OTC in watermeal and water by the seven-striped carp (Probarbus jullieni). They show, for the first time, the extent to which OTC is able to transfer from water to plant to fish and enter the food chain. The mean bioconcentration factor (dry weight basis) with watermeal was 1.28 × 10³ L kg⁻¹. Separate experiments were undertaken to characterize accumulation of OTC by carp from water and watermeal. These showed the latter pathway to be dominant under the conditions employed. The bioconcentration and biomagnification factors for these processes were 1.75 L kg⁻¹ and 2 × 10⁻⁴ kg g⁻¹ respectively. Using an aqueous concentration range of 0.34–3.0 μg L⁻¹, hazard quotients for human consumption of contaminated fish of 1.3 × 10⁻² to 1.15 × 10⁻¹ were derived.     

Distribution of organophosphate insecticides in a Thai biomass-water system

Sorption and leaching of the organophosphate (OP) pesticides chlorpyrifos, profenofos, methyl parathion and malathion were investigated with four different types of biomass: coconut husk, rice husk, peat moss and peanut shell. Organic carbon contents of the biomass were in the range of 35.4-45.4%. Sorption studies were carried out by the batch (equilibrium) method at 4 different OP spike concentrations and at pH 3-7. Sorption isotherms conformed to a linear Freundlich equation and the Freundlich constant or sorption coefficient (KD) confirmed that biomass organic carbon content was the principal sorbent factor affecting OP sorption. For a given sorbent, correlation of the extent of sorption with sorbate chemical properties was examined. Column leaching experiments involving different masses of coconut husk and peanut shell pre-spiked with OPs at the level equivalent to actual spraying concentrations in some Thai tangerine orchards were conducted. These experiments included repeated spikings and leaching. A water flow rate of 20 mL min(-1) was employed corresponding to the current average watering regime. Retardation and biodegradation with these sorbents were also examined.     

Geochemical partitioning of copper, lead, and zinc in benthic, estuarine sediment profiles

The geochemical partitioning of copper (Cu), lead (Pb), and zinc (Zn) was examined in benthic sediment profiles (0- to 20-cm depth interval) composed of relatively coarse (65-90% sand-sized particles), noncohesive, suboxic material (Eh +120 to +260 mV). Total Cu, Pb, and Zn concentrations ranged from 8.3 to 194, 16.3 to 74.8, and 30.1 to 220 mg/kg, respectively, and were related to vertical trends in sediment texture. The observed distribution coefficients describing solid-solution partitioning were in the range of 100 to 1000 L/kg. The geochemical partitioning of solid-phase Cu, Pb, and Zn between six operationally defined fractions was examined with a sequential extraction scheme. The association of Cu, Pb, and Zn with amorphous oxides, crystalline oxides, and organic matter was linearly dependent on the abundance of each respective phase. For retention by amorphous oxide minerals, the observed stoichiometry ranged from 5.2 to 23.7 mg/g for Cu, 12.8 to 21.5 mg/g for Pb, and 23.1 to 85.7 mg/g for Zn. Corresponding values for association with crystalline oxides were an order of magnitude less than those for amorphous oxides, indicating a lesser affinity of trace metals for crystalline oxides. The stoichiometric relationships describing association with organic matter ranged from 17.6 to 54.0 mg/g for Cu, 6.1 to 9.6 mg/g for Pb, and 6.4 to 16.4 mg/g for Zn. The results from this study provide an insight into processes controlling trace metal partitioning in coarse-textured, suboxic, estuarine sediments.     

Passive air sampling theory for semivolatile organic compounds

The mathematical modelling underlying passive air sampling theory can be based on mass transfer coefficients or rate constants. Generally, these models have not been inter-related. Starting with basic models, the exchange of chemicals between the gaseous phase and the sampler is developed using mass transfer coefficients and rate constants. Importantly, the inter-relationships between the approaches are demonstrated by relating uptake rate constants and loss rate constants to mass transfer coefficients when either sampler-side or air-side resistance is dominating chemical exchange. The influence of sampler area and sampler volume on chemical exchange is discussed in general terms and as they relate to frequently used parameters such as sampling rates and time to equilibrium. Where air-side or sampler-side resistance dominates, an increase in the surface area of the sampler will increase sampling rates. Sampling rates are not related to the sampler/air partition coefficient (K(SV)) when air-side resistance dominates and increase with K(SV) when sampler-side resistance dominates.     

Tributyltin partitioning in sediments: effect of aging

The effect of aging on the solid/pore-water partitioning and desorption behaviour of tributyltin (TBT) in sediments was examined. Three sediment samples with contrasting physical and chemical properties were spiked with 10 mg/kg TBT and aged under sterile conditions for periods of time ranging from 1 to 84 days. Aging had a negligible effect on partitioning and desorption behaviour in a sandy sample with very low organic carbon content (0.2% w/w). In contrast, for samples with larger amounts of organic carbon (2.6% and 4.8% w/w), aging caused substantial increases in TBT sorption. For these samples, apparent distribution coefficients (KD,app) obtained from sequential 2 h desorption experiments also exhibited a twofold increase between spiked sediments subjected to aging for 1 day and 84 days. This study demonstrates that aging effects may be an important aspect of TBT fate in contaminated sediments.     

Trace Metal Distribution and Enrichment in Benthic, Estuarine Sediments: Southport Broadwater, Australia

The distribution and enrichment of selected trace metals (Cd, Cr, Cu, Ni, Pb, Sn, Zn) in benthic sediments of the Southport Broadwater, a semi-enclosed coastal body of water adjacent to the Gold Coast city, south-eastern Queensland, Australia, was studied with the objective of assessing the extent and degree of sediment contamination. Sediment samples from the 0–10 cm and 10–20 cm depth intervals of 32 sites within the Southport Broadwater and surrounding residential canals were analysed for particle size distribution, pH, organic C and ‘near-total’ major (Al, Ca, Fe, Mn) and trace (Cd, Cr, Cu, Ni, Pb, Sn, Zn) metal contents. Sediment contamination for each trace metal was assessed by (1) comparison with Australian sediment quality guidelines, (2) calculation of the index of geoaccumulation based on regional background values, and (3) geochemical normalisation against Al (i.e. the abundance of alumino-silicate clay minerals). Based on this approach, the results indicate that submerged sediments in the study area are not presently enriched with Cd, Cr or Ni, with the spatial distribution of these metals being very well explained by the abundance of alumino-silicate clay minerals. However, several sites were strongly enriched with Cu, Pb, Sn and Zn, arising from sources related to either urban runoff or vessel maintenance activities. The study indicates that several varying approaches are needed for a satisfactory assessment of contaminant enrichment in estuarine sediments.     

Metal accumulation in aquatic macrophytes from southeast Queensland,Australia

To determine the extent of metal accumulation in some aquatic macrophytes from contaminated urban streams in southeast Queensland, plants were sampled from six sites, along with contiguous sediments. In all, 15 different species were collected, the most common genera being Typha (Cattails or Bulrushes) and Persicaria (Knotweeds). Before heavy metal analysis, plants were further separated into various morphological tissues, and five selected samples were separated into various physiological tissues. The cadmium, copper, lead and zinc content of the plants were analysed using flames AAS. In general, plant roots exhibited higher metal concentrations than the contiguous sediments. Of the metals of interest, only for zinc was there a relatively clear pattern of increasing accumulation in aquatic macrophytes with increasing sediment metal concentrations. Comparison between morphological tissues of the sampled plants found that roots consistently presented higher metal concentrations than either the stems or leaves, however unlike previous studies, this investigation revealed no consistent trend of stems accumulating more metals than the leaves. For Typha spp., metal concentrations followed the order of roots > rhizomes > leaves, while for Persicaria spp. the order was roots > leaves > stems. The submerged species Myriophyllum aquaticum accumulated the highest levels of metals overall (e.g. Zn 4300 micrograms g-1 dry weight and Cd 6.5 micrograms g-1), and the emergent macrophytes also exhibited relatively high metal contents in their roots. The leaves of the submerged and floating-leafed species collected contained relatively high quantities of the four metals of interest, compared with the leaves of emergent aquatic macrophytes. In the Typha rhizome and Persicaria stem samples analysed for internal variation in metal content, there was a pattern of increasing metal concentrations towards the external sections of the stem, both for subterranean stems (rhizomes) and above-substrate stems. For Persicaria stems, no clear pattern was observed for cadmium and lead, the two metals investigated that are not required by plants for survival.     

Prediction of bioconcentration factors under non-equilibrium conditions

With the bioconcentration of lipophilic compounds by aquatic organisms when equilibrium between water and biota is attained, the logarithm of the bioconcentration factor has a direct linear relationship with the logarithm of the octanol/water partition coefficient. In practice, however, equilibrium may not be reached, particularly for more lipophilic compounds. It is shown theoretically, and confirmed by use of published experimental results on fish, that a different direct linear relationship also exists between the logarithms of the bioconcentration factor and the partition coefficient for compounds not achieving equilibrium after a specific exposure time. Thus, non-equilibrium bioconcentration factors can be predicted from their partition coefficients. The constants in the non-equilibrium linear equation are related to those from the relationships between equilibrium bioconcentration factors and the partition coefficients, and between the first-order clearance rate constants and the partition coefficients.     

In-situ partitioning of butyltin compounds in estuarine sediments

The in-situ solid/pore-water partitioning of tributyltin (TBT), dibutyltin (DBT) and monobutyltin (MBT) was determined for an estuarine sediment profile collected from a commercial marina. Total butyltin levels exceeded sediment quality guideline values, and were 220-8750 microg/kg for TBT, 150-5450 microg/kg for DBT and 130-4250 microg/kg for MBT. Pore-water butyltin concentrations ranged from 0.05 to 2.35 microg/l for TBT, 0.07-3.25 microg/l for DBT, and 0.05-0.53 microg/l for MBT. The partitioning of butyltin compounds between the sediment solid-phase and pore-water was described by an organic carbon normalised distribution ratio (D(OC)). The observed D(OC) values were similar for TBT, DBT and MBT, and were 10(5)-10(6) l/kg. Values for the Butyltin Degradation Index (BDI) were larger than 1 at depths greater than 10 cm below the sediment/water-column interface. This indicates that substantial TBT degradation has occurred in the sediments, and suggests that natural attenuation may be a viable sediment remediation strategy.