Monitoring of the booster biocide dichlofluanid in water and marine sediment of Greek marinas

Dichlofluanid (N-dichlorofluoromethylthio-N'-dimethyl-N-phenylsulphamide) is used as booster biocide in antifouling paints. The occurrence of dichlofluanid and its metabolite DMSA (N'-dimethyl-N-phenyl-sulphamide) was monitored in seawater and marine sediment from three Greek marinas. Seawater and sediment samples were collected at three representative positions and one suspected hotspot in each marina and shipped to the laboratory for chemical analysis. As part of the project, an analytical method had been developed and validated. Furthermore, some additional experiments were carried out to investigate the potential contribution of paint particle bound dichlofluanid on the total concentration in the sediment. As expected, given its known high hydrolytic degradation rate, no detectable concentrations of dichlofluanid were measured in any of the seawater samples. DMSA was detected in seawater samples at very low concentrations varying from <3 ng l(-1) (LOD) to 36 ng l(-1). During method validation, it had already been demonstrated that dichlofluanid is unstable in sediment and can therefore only be determined as its metabolite DMSA. In a separate experiment, in which marine sediment was spiked with artificial paint particles containing dichlofluanid and then analysed according to the validated method, it was demonstrated that if there is any dichlofluanid originating from paint particles, this would be determined as DMSA. No DMSA was detected in any of the sediment samples. It could therefore be concluded that there were no significant concentrations of dichlofluanid in the sediment samples.     

Applicability of Fenton and H2O2/UV reactions in the treatment of tannery wastewaters

In this paper we evaluated the H2O2/UV and the Fenton's oxidation processes for the treatment of tannery wastewater under different experimental conditions. Efficiencies were judged by the amounts of organic substances degraded or eliminated under these treatment techniques. Daphnia magna and Vibrio fischeri were used to monitor toxicity. Organic compounds contained in the untreated and treated tannery wastewater were determined and identified using substance specific techniques. Gas chromatography-mass spectrometry (GC-MS) in positive electron impact (EI(+)) mode was applied to determine volatile organics. Atmospheric pressure ionization (API) mass (MS) and tandem mass spectrometry (MS-MS) coupled with flow injection analysis (FIA) or liquid chromatography (LC) were used to detect or identify polar organic pollutants. The experimental results indicated that both oxidation processes--H2O2/UV at pH 3 and Fenton at pH 3.5--are able to reduce TOC content by mineralisation of the organic compounds.     

Feral swine disturbance at important archaeological sites

Feral swine are well known as environmentally destructive invasive animals in many areas around the world, where they degrade native habitats, harm rare plant and animal species, damage agricultural interests, and spread disease. We provide the first quantification of their potential as agents of disturbance at archaeological sites. Our study was conducted in south-central Florida at Avon Park Air Force Range, a base comprising over 40,000 ha and containing many archaeological sites. To determine the identifiable prevalence of feral swine disturbance, we examined 36 sites registered with the Florida State Historic Preservation Office and also eligible for inclusion in the National Register of Historic Places (NRHP). Moreover, we evaluated the extent of swine disturbance at a prehistoric site of extraordinary significance to Florida’s prehistory, “Dead Cow.” Fifteen of the 36 NRHP-eligible sites (42 %) had some level of swine disturbance, including 14 of 30 (47 %) sites known to have artifacts within 20 cm of the surface (well within swine rooting depths). At the Dead Cow site, we documented disturbance at 74 % of shovel test points. Sites with shallow artifact depositions appeared highly vulnerable to disturbance by feral swine, threatening destruction of artifact stratigraphy and provenience. Our observations likely are a minimal representation of accumulated damage. These irreplaceable sites tell the area’s land use story across the millennia. That they are under threat from feral swine should serve broad notice of potential threats that feral swine may pose to archaeological sites globally, making effective swine management imperative for site protection.     

Contaminated sediments and bioassay responses of three macroinvertebrates, the midge larva Chironomus riparius, the water louse Asellus aquaticus and the mayfly nymph Ephoron virgo

Bioassays are widely used to estimate ecological risks of contaminated sediments. We compared the results of three whole sediment bioassays, using the midge larva Chironomus riparius, the water louse Asellus aquaticus, and the mayfly nymph Ephoron virgo. We used sediments from sixteen locations in the Dutch Rhine-Meuse Delta that differed in level of contamination. Previously developed protocols for each bioassay were followed, which differed in sediment pretreatment, replication, and food availability. The Chironomus bioassay was conducted in situ, whereas the other two were conducted in the laboratory. The measured endpoints, survival and growth, were related to contaminant levels in the sediment and to food quantity in water and sediment.

Only the response of A. aquaticus in the bioassay was correlated with sediment contamination. Food availability in overlying water was much more important for C. riparius and E. virgo, thereby masking potential sediment contaminant effects. We conclude that growth of A. aquaticus was depressed by sediment contamination, whereas growth of E. virgo and C. riparius was stimulated by seston food quantity. We discuss that the trophic state of the ecosystem largely affects the ecological risks of contaminated sediments.     

Temporal trends of organochlorine contamination in Black Guillemots in Iceland from 1976 to 1996

The levels of several different persistent organochlorines (OCs) in Black Guillemots Cepphus grylle, collected during the summers of 1976-1996 at Breioafj?rour in W-Iceland, were investigated. The levels of about 40 different organochlorines (PCBs, DDTs, chlordanes, toxaphenes, HCH, HCB) were compared with respect to age, sex, fat content, and year of collection. The levels of PCBs correlated very closely with those of DDE, indicating long-range transport as the major source of these contaminants in Iceland, with the ratio PCBs/DDE mostly in the range of 2-5. Unlike the Gyrfalcon Falco rusticolus, the organochlorine levels did not seem to accumulate substantially with age, neither in males nor females. The variation in the levels of OCs at the age of 2 years was even greater than the variation in OC levels over an age range of 12 years. In immature birds the levels of PCBs, DDE, HCB and beta-HCH declined very slowly (T(1/2) from 12 to 20 years) over the years 1976-1996, whereas the levels of alpha-HCH and p,p'-DDT declined much faster. The levels of trans-nonachlor, alpha-chlordane, gamma-chlordane, oxychlordane, and toxaphene did not correlate with the year of collection. As the Black Guillemot is mostly a resident seabird, feeding mainly on small fish and invertebrates, this investigation should give a good indication of the temporal trends of organochlorine pollution at Breioafj?rour, Iceland, during this 20 year period and is likely to reflect baseline trends in the marine environment of the North-Atlantic Ocean.     

Treatment of chlorinated solvents by TiO2 photocatalysis and photo-Fenton: influence of operating conditions in a solar pilot plant

Titanium dioxide photocatalysis (using 20 0mg l(-1) of TiO2), under aerobic and anaerobic conditions, and photo-Fenton (2 and 56 mg l(-1) iron) were applied to the treatment of different NBCS (non-biodegradable chlorinated solvents), such as dichloroethane, dichloromethane and trichloromethane dissolved in water at 50 mg l(-1). All the tests were performed in a 35-l solar pilot plant with compound parabolic collectors (CPCs) under natural illumination. The two solar treatments were compared with attention to chloride release and TOC mineralisation, as the main parameters. Photo-Fenton was found to be the more appropriate treatment for these compounds, assuming volatilisation as a drawback of photocatalytic degradation of NBCS dissolved in water. In this context, several operating parameters related to NBCS degradation, e.g., treatment time, temperature, hydrogen peroxide consumption and volatility of parent compounds are discussed. The correct choice of operating conditions can very often diminish the problem of volatilisation during treatment.     

Laboratory simulation of biodegradation of chemicals in surface waters: closed bottle and respirometric test

Microbial degradation is the most dominant elimination mechanism of organics from the environment. For evaluation of biodegradability of pure chemicals many standardized tests are available, but no standardized procedure for assessment of biodegradability of chemicals in surface water is agreed upon. Rates of in-situ biodegradation are usually estimated in laboratory simulation where environmental factors are reproduced to some extent. The aim of our study was to compare standardised ready biodegradability assessment, test (Closed bottle test) and its modifications employing the basic agreements on test conditions to simulate biodegradation in surface water. Standard test was modified using various natural river waters to simulate the natural environment in a simplified way. The impact of different types and amounts of nutrients and microorganisms on biodegradation was confirmed. The conditions in the recipient should be examined to extrapolate the results from ready biodegradability tests to real surface water.     

Tissue distribution of planar and non-planar chlorobiphenyls, 4,4'-DDE and hexachlorobenzene in sheep and lambs

The bioconcentration and distribution pattern of individual PCB congeners (IUPAC Nos: -54, -80, -155 and -169) and organochlorine pesticides (HCB and 4,4'-DDE) in blood, adipose tissue, liver and brain were examined in sheep two months after administration and in their offspring continuously exposed during the two months lactation period. Analyses were performed by high resolution gas chromatography. The levels of individual organochlorines varied significantly between tissues; the tissue/blood ratio (on a fat basis) varied by two orders of magnitude for individual congeners. The bioconcentration of the toxic planar PCB-169 congener was the highest in the liver and the lowest in the brain of the sheep.     

Metabolism and body-burden of PCBs in lactating dairy cows.

This paper uses data from a detailed 4 month PCB mass balance study on lactating cows fed a naturally contaminated background diet to quantify the metabolism and body-burdens of a range of PCB congeners. Dietary intake fluxes and milk and faecal output fluxes reported previously are combined with subcutaneous fat and blood PCB concentrations and with data from tissue/organ samples from a slaughtered animal to estimate the degree of metabolism within the cow. A total body burden is derived, showing that fat deposits account for approximately 98% of total PCB present in the lactating cow. The daily intake through feed (ng day-1) accounted for between 0.9 and 1.5% of the total body burden for persistent congeners (e.g. PCB 153) and up to 43% for those congeners which are readily metabolised (e.g. PCB 52). Detailed balances for a range of tri- to octa-chlorinated PCBs are presented and clearly demonstrate that many congeners are metabolised effectively by lactating dairy cows (e.g. PCB 149) whilst others are efficiently transferred to human dairy food products. An approach to predicting the degree of metabolism for individual PCB congeners is presented which gives good agreement with observations.