Dioxin- and POP-contaminated sites—contemporary and future relevance and challenges

BACKGROUND, AIM AND SCOPE: Once they have been generated, polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) and other persistent organic pollutants (POPs) can persist in soils and sediments and in waste repositories for periods extending from decades to centuries. In 1994, the US EPA concluded that contaminated sites and other reservoirs are likely to become the major source of contemporary pollution problems with these substances. With this in mind, this article is the first in a new series in ESPR under the title 'Case Studies on Dioxin and POP Contaminated Sites--Contemporary and Future Relevance and Challenges', which will address this important issue. The series will document various experiences from sites contaminated with PCDD/F and other POPs. This article provides an overview of the content of the articles comprising the series. In addition, it provides a review of the subject in its own right and identifies the key issues arising from dioxin/POP-contaminated sites. Additionally, it highlights the important conclusions that can be drawn from these examples. The key aim of this article and of the series as a whole is to provide a comprehensive overview of the types of PCDD/F contaminated sites that exist as a result of historical activities. It details the various processes whereby these sites became contaminated and attempts to evaluate their contemporary relevance as sources of PCDD/Fs and other POPs. It also details the various strategies used to assess these historical legacies of contamination and the concepts developed, or which are under development, to effect their remediation. MAIN FEATURES: Special sessions on 'Contaminated sites--Cases, remediation, risk and policy' were held at the DIOXIN conferences in 2006 and 2007, and this theme will be continued at DIOXIN 2008 to be held in Birmingham. Selected cases from the approximately 70 contributions made to these sessions, together with some additional invited case studies are outlined together with the key issues they raise. By evaluating these cases and adding details of experiences published in the current literature, an overview will be given of the different features and challenges of dioxin and POP-contaminated sites. RESULTS: This article provides a systematic categorisation of types of PCDD/F and POP-contaminated sites. These are categorised according to the chemical or manufacturing process, which generated the PCDD/Fs or POPs and also includes the use and disposal aspects of the product life cycle in question. The highest historical PCDD/F and dioxin-like polychlorinated biphenyl (PCB) contamination burdens have arisen as a result of the production of chlorine and of chlorinated organic chemicals. In particular, the production of chlorinated pesticides, PCBs and the related contaminated waste streams are identified being responsible for historical releases of toxic equivalents (TEQs) at a scale of many tonnes. Along with such releases, major PCDD/F contaminated sites have been created through the application or improper disposal of contaminated pesticides, PCBs and other organochlorine chemicals, as well through the recycling of wastes and their attempted destruction. In some extreme examples, PCDD/F contaminated sites have also resulted from thermal processes such as waste incinerators, secondary metal industries or from the recycling or deposition of specific waste (e.g. electronic waste or car shredder wastes), which often contain chlorinated or brominated organic chemicals. The examples of PCDD/F and dioxin-like PCB contamination of fish in European rivers or the impact of contaminated sites upon fishing grounds and upon other food resources demonstrate the relevance of these historical problems to current and future human generations. Many of the recent food contamination problems that have emerged in Europe and elsewhere demonstrate how PCDD/F and dioxin like PCBs from historical sources can directly contaminate human and animal feedstuffs and indeed highlight their considerable contemporary relevance in this respect. Accordingly, some key experiences and lessons learnt regarding the production, use, disposal and remediation of POPs from the contaminated sites are summarised. DISCUSSION: An important criterion for evaluating the significance and risks of PCDD/Fs and other POPs at contaminated sites is their present or future potential for mobility. This, in turn, determines to a large degree their propensity for off-site transport and environmental accessibility. The detailed evaluation of contaminated site cases reveals different site-specific factors, which influence the varied pathways through which poor water-soluble POPs can be mobilised. Co-contaminants with greater water solubility are also typically present at such sites. Hence, pumping of groundwater (pump and treat) is often required in addition to attempting to physically secure a site. At an increasing number of contaminated sites, securing measures are failing after relatively short time spans compared to the time horizon, which applies to persistent organic pollutant contamination. Due to the immense costs and challenges associated with remediation of contaminated sites 'monitored natural attenuation' is increasingly gaining purchase as a conceptual remediation approach. However, these concepts may well prove limited in their practical application to contaminated sites containing persistent organic pollutants and other key pollutants like heavy metals. CONCLUSIONS: It is inevitable, therefore, that dioxin/POP-contaminated sites will remain of contemporary and future relevance. They will continue to represent an environmental issue for future generations to address. The securing and/or remediation of dioxin/POP-contaminated sites is very costly, generally in the order of tens or hundreds of millions of dollars. Secured landfills and secured production sites need to be considered as constructions not made for 'eternity' but built for a finite time scale. Accordingly, they will need to be controlled, supervised and potentially repaired/renewed. Furthermore, the leachates and groundwater impacted by these sites will require ongoing monitoring and potential further remediation. These activities result in high maintenance costs, which are accrued for decades or centuries and should, therefore, be compared to the fully sustainable option of complete remediation. The contaminated site case studies highlight that, while extensive policies and established funds for remediation exist in most of the industrialised western countries, even these relatively well-regulated and wealthy countries face significant challenges in the implementation of a remediation strategy. This highlights the fact that ultimately only the prevention of contaminated sites represents a sustainable solution for the future and that the Polluter Pays Principle needs to be applied in a comprehensive way to current problems and those which may emerge in the future. RECOMMENDATIONS AND PERSPECTIVES: With the continuing shift of industrial activities in developing and transition economies, which often have poor regulation (and weak self-regulation of industries), additional global challenges regarding POPs and other contaminated sites may be expected. In this respect, a comprehensive application of the "polluter pays principle" in these countries will also be a key to facilitate the clean-up of contaminated areas and the prevention of future contaminated sites. The threats and challenges of contaminated sites and the high costs of securing/remediating the problems highlight the need for a comprehensive approach based upon integrated pollution prevention and control. If applied to all polluting (and potentially polluting) industrial sectors around the globe, such an approach will prove to be both the cheapest and most sustainable way to underpin the development of industries in developing and transition economies.     

In utero ultrasonographic features of campomelic dysplasia

A prenatal diagnosis of campomelic dysplasia in a primigravida is described. First level fetal ultrasonography demonstrated bowing and shortening of lower limbs. Second level examination allowed the correct diagnosis by demonstrating several skeletal anomalies pathognomonic of campomelic dysplasia.     

Preliminary investigation on the environmental occurrence and effects of antibiotics used in aquaculture in Italy

A preliminary investigation has been carried out on the occurrence and effects of antibiotics used in Italian aquaculture with the objective of identifying priorities for monitoring programmes. According to the information available on the most pertinent and diffuse fish diseases and their related therapies, the presence of flumequine and oxytetracycline in sediments sampled from two trout farms and three sea-bass farms and in their surrounding environments was selected for an analytical investigation. The concentrations of oxytetracycline and flumequine varied up to a maximum of 246.3 and 578.8 microg/kg d.w., respectively. Flumequine was seen to have the highest toxicity in a bioluminescence assay with EC50 values varying within the range of 12-15 mg/l, while the EC50 values for oxytetracycline were within the range of 121-139 mg/l. The results of the present study indicate flumequine and oxytetracycline as priority chemicals to be monitored for possible environmental side effects of aquaculture in Italy. Apart from peak concentrations the chronic presence of flumequine and oxytetracycline in sediments both inside and outside farms should also be considered. In spite of the potential risks related to the use of antibiotics, the concentrations found in the sediments of the studied fish farms are significantly lower than those found in other areas.     

Hair mercury levels in an urban population from southern Italy: fish consumption as a determinant of exposure

Mercury levels in hair of a general population, 237 adults aged between 35-45, in Naples, Italy, were assessed. The subjects were asked to fill in a questionnaire about age, gender, body weight, height, body mass index (BMI), fish consumption, number, surface and area of dental amalgam fillings. Total mercury (THg) concentrations in human hair ranged from 0.221 to 3.402 microg/g and the mean value for the subjects under study was 0.638 microg/g. Study participants were divided into three groups in accordance with fish consumption and dental amalgam: ANF (amalgam and no fish); NAF (no amalgam but with fish) and AAF (amalgam and fish). Significant differences in THg were found in the three groups (p<0.05). A multiple linear regression analysis showed a weak but significant correlation of THg content in hair with respect to gender and age, but almost no association was found between THg and dental fillings. Conversely, a strong correlation was obtained between THg and fish consumption regardless of the group evaluated. Finally, mercury levels in hair exceeded the levels corresponding to the EPA reference dose (RfD) of 0.1 microg Hg/kg body weight per day (1 microg Hg/g hair) in 6% of the population (4% men and 2% women). However, the THg limits in our subjects were not exceeded according to the WHO guidelines, which use a benchmark dose of 0.23 microg Hg/kg bw/day (14 microg Hg/g maternal hair).     

Valuation of Ecological Resources and Functions

/ Ecological resources are natural resources that provide certain necessary but overlooked system maintenance functions within ecosystems. Environmental economics is in search of an appropriate analysis framework to determine economic values of such resources. This paper presents a framework that estimates and compiles the components of value for a natural ecosystem. The framework begins with the ecological processes involved, which provide functions within the ecosystem and services valued by humans. We discuss the additive or competive nature of these values, and estimate these values through conventional and unconventional techniques. We apply the framework to ecological resources in a shrub-steppe dryland habitat being displaced by development. We first determine which functions and services are mutually exclusive (e.g., farming vs soil stabilization) and which are complementary or products of joint production (e.g., soil stabilization and maintenance of species). We then apply benefit transfer principles with contingent valuation methodology (CVM), travel cost methodology (TCM), and hedonic damage pricing (HDP). Finally, we derive upper-limit values for more difficult-to-value functions through the use of human analogs, which we argue are the most appropriate method of valuation under some circumstances. The highest values of natural shrub-steppe habitat appear to be derived from soil stabilization.KEY WORDS: Natural resource economics; Ecological economics; Ecological resources; Shrub-steppe; Environmental valuation; Cost; Benefit; Value     

Effects of salinity on the clam <Emphasis Type="Italic">Chamelea gallina</Emphasis> haemocytes. Part II: Superoxide dismutase response

The effects of different salinity levels (28, 34 and 40‰) on functional responses of Chamelea gallina haemocytes were evaluated in a two part study dealing with modulations of immune parameters. This part (Part II) of the study was focused on the superoxide dismutase (SODs) activity and expression in haemocyte lysate and cell-free haemolymph. Results of this study established that the exposure of C. gallina specimens at 40‰ salinity provoked a decrease in Mn-SOD and Cu/Zn-SOD activities in haemocyte lysate suggesting a declining superoxide anion generation at the highest salinity tested. Expression of MnSOD was coherent with activity values, while Cu/ZnSOD showed two immunoreactive bands. The former corresponds to the cytosolic Cu/Zn-SOD (16 kDa) was not coherent with the enzyme activity and the second (28–30 kDa) probably attributed to EC-SOD. In cell-free haemolymph, Mn-SOD activity decrease and Cu/Zn-SOD activity increase at 40‰ were observed, likely due to EC-SOD contribution, strongly induced at the same salinity. After EC-SOD detection with two different antibody, we postulate that the EC-SOD like-protein band (29 kDa) may be constitute partly by EC-SOD and probably by Cu/Zn-SOD dimeric form not completely dissociated under reducing condition or a Cu/Zn-SOD degenerated but still recognized by antibody. The cell-free haemolymph increase of EC-SOD at high salinity values plays an important role in immune defence of C. gallina. According to the conclusion of Part I of this study, our data confirmed the destabilizing effect of 40‰ salinity on haemocyte functionality, while to 28‰ exposure, data don’t confirm its stressful action as instead stated by results of Part I. Further studies are necessary to clear up this discrepancy.     

Effects of salinity on the clam <Emphasis Type="Italic">Chamelea gallina</Emphasis>. Part I: alterations in immune responses

In the present study, the effects of differing salinities on some important functional responses of haemocytes from the clam, Chamelea gallina, were investigated. The animals were kept for 7 days at 28‰ (hyposalinity), 34‰ (control) and 40‰ salinity (hypersalinity), and total haemocyte count (THC), haemocyte volume, phagocytosis, lysozyme-like activity (in both haemocyte lysate and cell-free haemolymph) were measured. The survival-in-air test was also performed. Clams kept at 28‰ showed significantly increased THC with respect to animals kept at 34 and 40‰. The analysis of haemocyte size frequency distribution highlighted that in clams kept at 28‰ the haemocyte fraction of about 5 μm in diameter and 50–100 femtolitre in volume increased markedly. Conversely, in animals kept at 40‰ an increase was observed in the haemocyte fraction having about 8–10 μm diameter and 400–500 femtolitre volume. Higher phagocytic activity was recorded in haemocytes from control clams, with respect to that of clams kept at 28 and 34‰. Lysozyme-like activity in haemocyte lysate was shown to increase significantly in animals kept at 28‰ with respect to that of clams kept at 40‰, whereas enzyme activity in cell-free haemolymph from clams kept at 34‰ was significantly higher with respect to that of clams maintained at 40‰. A relationship between phagocytosis and lysozyme secretion is suggested. The resistance to air exposure of clams kept at 28 and 40‰ was shown to decrease significantly; LT₅₀ values fell from 7 days in clams kept at 34‰ to 4 and 5 days in those kept at 28 and 40‰, respectively. Results demonstrated that salinity values far from 34‰ affects the functional responses of haemocytes and reduce the resistance of clams to exposure to air.     

Meiofauna densities and gastrotrich community composition in a Mediterranean sea cave

During the past 5 decades, the large-sized biota inhabiting dark marine caves has attracted the attention of many marine biologists; in contrast, studies concerning the meiofaunal organisms of these peculiar biotopes remain scanty and mostly with a taxonomic aim. In this study, the nature and abundance of meiofaunal taxa living in a Mediterranean, semi-submerged sea cave was surveyed in relation to distance from the entrance and over two different seasonal periods. Particular attention was paid to the Gastrotricha taxocene. Research was carried out in a cave along the Ionian coast of Apulia (southern Italy), the “Grotta Piccola del Ciolo” which opens for approximately 120 m on the north-eastern side of a shallow fjord and has a bottom blanketed by fine to very fine sand, occasionally rich in detritus. Quantitative samples in four replicates were collected by SCUBA diving, in November 2000 and June 2001, coring the sediment with a hand-held piston corer in three light-free sites (stations 1–3) located at increasing distances from the entrance. At each site, two additional 500-ml sediment samples were collected for an in vivo study of the Gastrotricha. Faunistic analysis found a fairly high meiobenthic diversity, identifying representatives of more than 12 major groups, with total abundances ranging from 656 ind./10 cm² (10 cm²) in November to 1,069 ind./10 cm² in June. Station 1, the closest to the entrance invariably hosted the most abundant meiofaunal community (851 ind./10 cm² in November and 1932 ind./10 cm² in June), followed by station 2 or 3 depending on the season. While nematodes and harpacticoids appear as the most abundant taxa when the cave is considered as a whole, other taxa may prevail numerically in selected stations, e.g. priapulids, which are the second most abundant taxon at station 1 (30 ind./10 cm² in November and 83 ind./10 cm² in June). Although the density of total meiofauna and that of the single groups may not be very high, the cave is interesting by virtue of the peculiarity of the hosted fauna, e.g., species and genera new to science or new to the Mediterranean Sea. Regarding the Gastrotricha, we found 16 species, accounting for 1.3–2.6% of the total meiobenthos (density = 8.4 ind./10 cm² in November and 27.4 ind./10 cm² in June). Analysis of the gastrotrich community found, particularly in June, an assemblage of taxa quite different from those found in open habitats, even at the family level; differences that are probably due to the exploitation of different food resources by animals populating the two environments, i.e. algae in the open sea versus bacteria in the caves. Results indicate that for meiofauna, as happens for macrofauna, the marine caves may represent hotspots of biodiversity and endemism; the driving forces at the base of the trophic depletion hypothesis seem to be responsible for structuring the meiofauna community inside the cave.     

Do male barn swallows (<Emphasis Type="Italic">Hirundo rustica</Emphasis>) experience a trade-off between the expression of multiple sexual signals?

Some sexual selection models envisage exaggerated male secondary sexual characters to be costly and therefore reliable indicators of the quality of potential mates to choosy females. If male secondary sexual characters have a natural selection cost, they may be linked to each other by reciprocally constraining relationships that would prevent individual males from increasing their level of multiple signaling. Barn swallow (Hirundo rustica) males have at least two costly signals relevant to socio-sexual interactions: tail length and song. Under the hypothesis that a trade-off exists between male signals, we manipulated the maintenance cost of tail ornaments to test whether this reduced the quantity and quality of song, a condition-dependent, phenotypically plastic signal. Contrary to our expectation, tail elongation had no effect on singing activity and song complexity. However, tail-elongated males produced songs with longer terminal parts ('rattles'). Long rattles are associated with highly competitive social contexts and high circulating levels of testosterone, suggesting that tail-elongated males were more frequently involved in either male-male aggressive or inter-sexual interactions. Therefore, this study shows that males are not displaying multiple signals at the maximum possible level, implying that this system is open to unreliable communication. However, long-term trade-offs between signal expression and viability may prevent males from displaying both signals at higher rates.Communicated by: M. Webster     

Effects of female mating status on copulation behaviour and sperm expenditure in the freshwater crayfish <Emphasis Type="Italic">Austropotamobius italicus</Emphasis>

Sperm competition models predict that males should adjust their sperm expenditure according to the risk and/or intensity of sperm competition. In this paper, we analysed copulatory behaviour of both sexes and sperm expenditure in relation to female mating status (virgin or mated) in the freshwater crayfish Austropotamobius italicus, a species where males have been reported to feed on and remove sperm laid by other males. The same females were allowed to be inseminated sequentially by two males, and we compared the sexual behaviours of partners between the first (virgin females) and the second mating (mated females). We found that female resistance did not differ between the first and the second mating, nor males refused or took more time to mount a mated female. However, when mating with a mated female, males reached an effective copulation position significantly later. This occurred because second-mating males removed, by eating, all or most spermatophores previously deposited by first males. As removal was often incomplete, this resulted in a larger amount of sperm being deposited on female ventral parts after the second mating, although second males did not allocate more sperm to mated females than first males did. Thus, the peculiar mode of sperm competition, where males remove previously deposited sperm, and the consequent predictable strong last male prevalence in paternity likely led to the observed lack of adjustment of sperm expenditure to female mating status in this species.