Risk assessment of trace elements in the stomach contents of Indo-Pacific Humpback Dolphins and Finless Porpoises in Hong Kong waters

The potential health risks due to inorganic substances, mainly metals, was evaluated for the two resident marine mammals in Hong Kong, the Indo-Pacific Humpback Dolphin (Sousa chinensis) and the Finless Porpoise (Neophocaena phocaenoides). The stomachs from the carcasses of twelve stranded dolphins and fifteen stranded porpoises were collected and the contents examined. Concentrations of thirteen trace elements (Ag, As, Cd, Co, Cr, Cs, Cu, Hg, Mn, Ni, Se, V and Zn) were determined by inductively coupled plasma mass spectrometer (ICP-MS). An assessment of risks of adverse effects was undertaken using two toxicity guideline values, namely the Reference Dose (RfD), commonly used in human health risk assessment, and the Toxicity Reference Value (TRV), based on terrestrial mammal data. The levels of trace metals in stomach contents of dolphins and porpoises were found to be similar. Risk quotients (RQ) calculated for the trace elements showed that risks to the dolphins and porpoises were generally low and within safe limits using the values based on the TRV, which are less conservative than those based on the RfD values. Using the RfD-based values the risks associated with arsenic, cadmium, chromium, copper, nickel and mercury were comparatively higher. The highest RQ was associated with arsenic, however, most of the arsenic in marine organisms should be in the non-toxic organic form, and thus the calculated risk is likely to be overestimated.     

Effects of flow regime and flooding on heavy metal availability in sediment and soil of a dynamic river system

The acid volatile sulphide (AVS) and simultaneously extracted metals (SigmaSEM) method is increasingly used for risk assessment of toxic metals. In this study, we assessed spatial and temporal variations of AVS and SigmaSEM in river sediments and floodplain soils, addressing influence of flow regime and flooding. Slow-flowing sites contained high organic matter and clay content, leading to anoxic conditions, and subsequent AVS formation and binding of metals. Seasonality affected these processes through temperature and oxygen concentration, leading to increased levels of AVS in summer at slow-flowing sites (max. 37micromolg(-1)). In contrast, fast-flowing sites hardly contained AVS, so that seasonality had no influence on these sites. Floodplain soils showed an opposite AVS seasonality because of preferential inundation and concomitant AVS formation in winter (max. 3-30micromolg(-1)). We conclude that in dynamic river systems, flow velocity is the key to understanding variability of AVS and SigmaSEM.     

Near Real-Time Monitoring and Mapping of Specific Conductivity Levels Across Lake Texoma, USA

A submersible sonde equipped with a specific conductivity probe, linked with a global positioning satellite receiver was developed, deployed on a small boat, and used to map spatial and temporal variations in specific conductivity in a large reservoir. 7,695 sample points were recorded during 8 sampling trips. Specific conductivity ranged from 442,uS/cm to 3,378,uS/cm over the nine-month study. The data showed five statistically different zones in the reservoir: 2 different riverine zones, 2 different riverine transition zones, and a lacustrine zone (the main lake zone). These data were imported to a geographic information system where they were spatially interpolated to generate 8 maps showing specific conductivity levels across the entire surface of the lake. The highly dynamic nature of water quality, due to the widely differing nature of the rivers that flow into the reservoir and the effect of large inflows of fresh water during winter storms is easily captured and visualized using this approach.     

Lichen and moss bags as monitoring devices in urban areas. Part II: trace element content in living and dead biomonitors and comparison with synthetic materials

Lobes of the lichen Pseudevernia furfuracea (L.) Zopf and shoots of the moss Hypnum cupressiforme Hedw. were subjected to different treatments (water washing, oven drying, HNO3 washing, NH4-oxalate extraction) to assess the influence of vitality on accumulation efficiency, during a 6-week exposure in bags in two Italian cities, Trieste and Naples. No trend emerged between treatments, in terms of accumulation ability, for major and trace elements. Only water-washed lichens showed an increased C and N content after exposure in both cities. Element concentrations generally reached higher values in mosses than in lichens, especially for Al, Fe, and Zn (both cities), and for Cu, Mg and Na (Naples). Surface development strongly influenced accumulation capacity of the biomonitors. Quartzose and cation exchange filters revealed, on a weight basis, a poor performance. In urban environments, surface interception of atmospheric particulate seems to play a major role in accumulation, irrespective of organism vitality.     

Determination of selected quaternary ammonium compounds by liquid chromatography with mass spectrometry. Part I. Application to surface, waste and indirect discharge water samples in Austria

A method for simultaneous quantitative determination of alkyl benzyl, dialkyl and trialkyl quaternary ammonium compounds (QACs) has been developed, validated and subsequently applied to real water samples in Austria. The method employs liquid-liquid extraction (LLE) followed by liquid chromatography/tandem mass spectrometry (LC-MS/MS), using electrospray ionization (ESI) in positive mode. The overall method quantification limits range from 4 to 19ng/L for the enrichment of 500mL water samples and analyte recoveries are between 80 and 99%. The method was applied to 62 of the respective water samples without filtration to avoid the loss of the analytes due to the high adsorption capacity of these compounds. Maxima in the mg/L range, especially in the wastewater of hospitals and laundries, could be detected for the selected target compounds.     

Biological denitrification of high strength nitrate waste using preadapted denitrifying sludge

Denitrification of synthetic high nitrate waste containing 9032 ppm NO(3)-N (40,000 ppm NO(3)) in a time period of only 6h has been achieved in our previous study using activated sludge. The activated sludge culture was acclimatized by a stepwise increase in the nitrate concentration of synthetic waste. In the present work, studies were carried out on the changing microbial population of the sludge and the physiology of nitrate metabolism during the various stages of adaptation process to high strength synthetic nitrate waste. During the course of adaptation, with an increase in the nitrate concentration, a sharp increase in the number of denitrifiers was found with an equally rapid decrease in the nitrifying community. Two key enzymes involved in the first two steps of the denitrification process were also studied during this period. The results of the study suggest that specific enzyme levels increase as the activated sludge adapts itself to higher nitrate concentrations. Biological denitrification of high nitrate waste is a slow process and to increase the rate of denitrification, parameters such as pH, temperature, C:N and biomass concentration of the process were optimized using orthogonal array method. Optimized conditions increased the specific nitrate reduction rate by 54% and specific nitrite reduction rate by 45%.     

Mobility of dimethoate residues from spring broccoli field

Dimethoate [O, O-dimethyl-S-(N-methylcarbamoyl-methyl) phosphorodithioate] is a broad-spectrum systemic insecticide currently used worldwide and on many vegetables in Kentucky. Dimethoate is a hydrophilic compound (log KOW = 0.7) and has the potential of offsite movement from the application site into runoff and infiltration water. The dissipation patterns of dimethoate residues were studied on spring broccoli leaves and heads under field conditions. Following foliar application of Dimethoate 4E on broccoli foliage at the rate of 0.47 L acre(-1), dimethoate residues were monitored in soil, runoff water collected down the land slope, and in infiltration water collected from the vadose zone. The study was conducted on a Lowell silty loam soil (pH 6.9) planted with broccoli under three soil management practices: (i) soil mixed with municipal sewage sludge, (ii) soil mixed with yard waste compost, and (iii) no-mulch rototilled bare soil. The main objective of this investigation was to study the effect of mixing native soil with municipal sewage sludge or yard waste compost, having considerable amounts of organic matter, on off-site movement of dimethoate residues into runoff and infiltration water following spring rainfall. The initial deposits of dimethoate were 6.2 and 21.4 micro g g(-1) on broccoli heads and leaves, respectively. These residues dissipated rapidly and fell below the maximum residue limit of 2 micro g g(-1) on the heads and leaves after 10 and 14 d, respectively, with half-lives of 5.7 d on broccoli heads and 3.9 d on the leaves. Dimethoate residues detected in top 15 cm of soil (due to droplet drift and wash off residues from broccoli foliage) one day (d) following spraying, were 30.5 ng g(-1) dry soil in the sewage sludge treatment, and 46.1 and 134.5 ng g(-1) dry soil in the yard waste and no mulch treatments, respectively. Water infiltration was greater from yard waste compost treatment than from no mulch treatment, however concentrations of dimethoate in the vadose zone of the three soil treatments did not differ.     

DDT in fish from the Bulgarian region of the Black Sea

In spite of a worldwide reduction in the utilization of organochlorine pesticides (OCPs), they are still a problem for the aquatic environment and human health. The Black Sea is still being polluted with persistent chemicals, including OCPs. Aquatic organisms (sprat, scad, bluefish, shad, belted bonito, goby, and black mussel) with different feeding behaviours were sampled on a seasonal basis from the Bulgarian region of the Black Sea, and the concentrations of 13 OCP residues were determined. Although many of the OCPs were not detected in the samples, in all samples 1,1,1-trichloro-2,2-bis(4-chlorophenyl) ethane (DDT) was present mainly in the form of its metabolites 1,1-dichloro-2,2-bis(4-chlorophenyl) ethane (DDD) and 1,1-dichloro-2,2-bis(4-chlorophenyl) ethylene (DDE). Only about 12% of the total DDT was present as the parent compound pp-DDT, which suggests that it was not being used recently in the region. The total DDT concentrations were generally below 150 μg kg^-1 fresh weight, but higher levels—up to 354 μg kg^-1 fresh weight—were also measured for fish species with a high fat content. Between-species differences were observed, even when the concentrations were presented on a fat-level basis. DDT concentrations did not show any significant changes over the 2-yr sampling period. Fish sampled in the northern areas of the Bulgarian Black Sea coast seemed to contain higher DDT levels than those from the southern areas, suggesting a major (historical) influence of the Danube River. For permanent monitoring purposes, the utility of Black Sea gobies and scad should be considered.