pp´DDT and pp´DDE Accumulation in a Food Chain of Lake Maggiore (Northern Italy): Testing Steady-State Condition

- DOI: http://dx.doi.org/10.1065/espr2006.01.010 Background, Aims and Scope Although pp'DDT usage was strongly limited or banned in most parts of the world during the last three or four decades, the parent compound, its homologues and their metabolites still occur at levels which might pose a risk for many ecosystem components. A case of DDT pollution of industrial origin was discovered in 1996 in Lake Maggiore, the second largest (212 km2) and deepest (370 m) lake in Italy, causing concern for wildlife and human health. The extensive monitoring of many biotic and abiotic compartments which followed from 1998 in order to assess the pollution level and its trend in time, provided a great availability of data referring to DDT contamination of the different fish species of the lake. In this study, the recent contamination levels in selected fish species were compared to those measured in 1998 to evaluate the temporal pollution trend of the lake and its natural recovery, given that no remediation measures were carried out on the contaminated soils and sediments in this time span. Moreover, a modelling approach to test the equilibrium condition between water and pelagic fish species was used. Analytical results of pp'DDT and pp'DDE concentrations in lake water were used as input data in the bioenergetic model by Connolly & Pedersen (1988) to calculate concentrations in two fish species and to compare the predicted and the measured contamination. Methods Sampling and analytical determination of DDT homologues in lake water: Five water sampling campaigns were carried out from May 2002 to February 2004 in three sampling sites of Lake Maggiore. Suspended and dissolved pollutants were determined separately. Quantitative DDT homologue analyses were performed by HRGC coupled with ECD detection by the external standard method. Single water extracts were put together in correspondence with the stratification zones of the water column inferred on the basis of the temperature profile to improve analytical sensitivity. Selection of fish data: Concentrations of DDT and DDE in fishes were selected from recent literature (CIPAIS 2003, 2004). Bioaccumulation model: The bioenergetic model proposed by Connolly & Pedersen (1988) was used to assess the bioaccumulation of pp'DDT and pp'DDE of Alosa fallax (landlocked shad) and Coregonus spp. (whitefish), selected among the different species as representative of a secondary consumer level. Results and Discussion The average concentrations of pp'DDT and pp'DDE in water to be used as input data in the bioenergetic model were obtained considering all the concentrations measured at the three sampling stations in the epylimnion where the fish species considered in this study spend most of their life. The resulting values were 0.05 and 0.16 ng/L for pp'DDT and pp'DDE, respectively. Average measured pp'DDT and pp'DDE concentrations in landlocked shad were 0.81 +/- 0.39 and 1.69 +/- 0.71 mg/kg lipids, respectively, and were 0.29 +/- 0.12 and 1.06 +/- 0.41 mg/kg lipids for the whitefish. Calculated and measured values turned out to be in quite good agreement for pp'DDT, while measured pp'DDE concentrations were higher than expected on the basis of the bioenergetic model in both species. Probably metabolic transformations of pp'DDT accumulated in fish tissues in the past are responsible for the observed differences between calculated and expected pp'DDE concentrations in fish. Conclusions Pelagic fishes of Lake Maggiore seem to maintain the DDT accumulated during their life time and the most efficient mechanism responsible for the fish population recoveries is probably their generation changes; for this reason, equilibrium models cannot be used until negligible pp'DDT concentrations are reached in fish tissues. Recommendations and Outlook The limit proposed for pp'DDT in water by the EU Directive 2000/60, which will come in force in 2008, is 0.2 ng/L, four times higher than the average concentration measured in Lake Maggiore waters. Nevertheless, concentrations measured in Lake Maggiore fish were very close and sometimes exceeded the Maximum residue limits (MRLs) settled by the Italian legislation for foods (0.1 mg/kg w.w. for fish containing 5–20% lipid). It seems, therefore, that the 'environmental quality standard' of 0.2 ng/L cannot guarantee the suitability of fish for human consumption.     

Arsenic uptake and accumulation in curly endives (Cichorium endivia L.) irrigated with contaminated water

Arsenic accumulation in vegetables for direct human consumption represents a concern for food safety purposes. This potential problem can be of economic importance particularly in much appreciated, high-quality horticultural products. In this work, a greenhouse set of experiments were conducted to evaluate possible phytotoxic effects and arsenic accumulation in the production of curly endives with arsenic contaminated water.Two concentration levels (0.5 mg/L and 1.0 mg/L) and two arsenic species (As+3 and As+5) were considered. Dry mass production tended to be reduced as As+3 concentration increased in irrigation water. However, As+5 treatments did not show significant dry mass production differences with a blank (control experiment). As accumulation in plant increased with As concentration in irrigation waters, following a linear trend. Nevertheless, the increase of accumulated As was not statistically significant for As+5 at 0.5 mg/L. Calculated biological absorption coefficients resulted in higher than previous values reported in the literature, which was attributed here to the source of arsenic (irrigation water). Considering field values for As+5/As+3 ratio and averaged concentrations in water, the obtained results support that there is not a short-or medium-term risk to food safety in the curly endive crop in the region of Castilla y León (Spain).     

Occurrence of carbon monoxide during organic waste degradation

The concentrations of carbon monoxide (CO) and other gases were measured in the emissions from solid waste degradation under aerobic and anaerobic conditions during laboratory and field investigations. The emissions were measured as room temperature headspace gas concentrations in reactors of 1, 30, and 150 L, as well as sucked gas concentrations from windrow composting piles and a biocell, under field conditions. The aerobic composting laboratory experiments consisted of treatments with and without lime. The CO concentrations measured during anaerobic conditions varied from 0 to 3000 ppm, the average being 23 ppm, increasing to 133 ppm when methane (CH4) concentrations were low. The mean/maximum CO concentrations during the aerobic degradation in the 2-L reactor were 101/194 ppm without lime, 486/2022 ppm with lime, and 275/980 ppm in the 150-L reactors. The presence of CO during the aerobic composting followed a rapid decline in O2 concentrations Significantly higher CO concentrations were obtained when the aerobic degradation was amended with lime, probably because of a more extreme depletion of oxygen. The mean/maximum CO concentrations under field conditions during aerobic composting were 95/1000 ppm. The CO concentrations from the anaerobic biocell varied from 20 to 160 ppm. The hydrogen sulfide concentrations reached almost 1200 ppm during the anaerobic degradation and 67 ppm during the composting experiments.     

Ecotoxicological effect of grounded MV River Princess on the intertidal benthic organisms off Goa

The ecotoxicological effects of oil spill from the grounded vessel MV River Princess on the intertidal benthic organisms of Sinquerim-Candolim beach at Goa were investigated. An intertidal expanse of 1 km on either side of the grounded vessel was selected to evaluate the concentration of total petroleum hydrocarbon (TPH) in the sediment and its effects on the composition, abundance and diversity of micro-, meio- and macrobenthos. TPH in the intertidal sediment ranged from 7.8 to 89 microg g(-1) (mean 35.44+/-26.35 SD). Microbenthos comprised of microalgae, protozoans and juvenile forms of meiobenthos. Apart from juvenile nematodes, which were abundant, Coscinodiscus spp., Navicula spp., and Nitzschia spp. representing microalgae were also observed in microbenthic samples. Meiobenthos was represented by 13 taxa and their total density ranged between 92 and 1057 nos. 10 cm(-2). Maximum meiobenthic abundance of 1057 nos. 10 cm(-2) was observed at Sinquerim. Nematodes were the dominant meiobenthic taxa followed by turbellarians and harpacticoid copepods. The macrobenthos was numerically dominated by polychaetes, followed by crustaceans whereas bivalve molluscs were less represented. There was substantial increase in the petroleum concentration in the beach sediment compared to the previously reported values and highest TPH (89 microg g(-1) sediment) values were in the vicinity of the grounded vessel. The polychaete/amphipod ratio and cumulative and partial dominance abundance-biomass curves showed significant negative impact of TPH on macrofauna. The benthic community structure also showed measurable changes, as there was significant decrease (60%) in the number of species. Given that the microalgal counts were low in sediment, it is assumed that the intertidal meiofauna was possibly using oil-degrading bacteria as alternate food source. In conclusion, the results reported here suggest that the grounded ore carrier is not only detrimental to the beach community, that may take longer time for recovery, but also affects the beach morphology which may have long-term impact on local fishery.     

Chlorinated paraffins: a review of analysis and environmental occurrence

Chlorinated paraffins (CPs), as technical mixtures of polychlorinated alkanes (PCAs), are ubiquitous in the environment. CPs tend to behave in a similar way to persistent organic pollutants (POPs), leading several countries to impose regulations on the use of CPs. In this article, we review the literature on the properties of CPs, the current analytical tools available to determine CPs in various types of environmental matrices, and concentrations found in the environment. In particular, concentrations of CPs in environmental compartments including air, water, sediments, biota, human food products and human tissues are summarized. Priorities for future research are: improvements in analytical methodologies (reducing the complexity of the analysis, producing reference materials and performing interlaboratory studies); determining background levels of chlorinated paraffins in the environment and human populations (this question should be answered using quality assured analytical tools allowing the intercomparison of data); and investigating the sources of CPs to the environment and to humans.     

Distribution and dissipation pathways of nonylphenol polyethoxylates in the Yellow River: Site investigation and lab-scale studies

Spatial distribution of nonylphenol polyethoxylates (NPEOs) and nonylphenol (NP) was investigated in a field study in Lanzhou Reach of the Yellow River. NPEOs and their metabolites were found in the river, with the maximum dissolved concentrations of 6.38 nmol/L for NPEOs, 0.19 nmol/L for nonylphenol ethoxy acetic acids (NPECs) and 0.79 nmol/L for NP, respectively. The maximum concentrations in the sediment and suspended particle samples were 1.50 and 5.09 nmol/g for NPEOs and NP, respectively. The effects of particles, light and microorganism on the dissipation of NPEOs in the river water were investigated based on lab-scale experiments. When natural particles were removed, 72% and 22% degradation of NPEOs were achieved at 120 h in non-sterile and sterile conditions with light, respectively. Different concentrations of NPECs were also observed in these experiments. When suspended particle matters (SPMs) were present, about 38-50% of NPEOs were sorbed to the particulate phase in only 1 h. As a result, the degradation of NPEOs and production of NPECs were inhibited. However, the combined sorption and degradation in the presence of SPMs resulted in lower dissolved NPEO concentrations than those in the absence of SPMs. Biodegradation was the most important pathway for NPEOs degradation in the river water, while NPECs seemed to be produced through both biological and abiological pathways.     

Naturally occurring radioactive material (NORM) from a former phosphoric acid processing plant

In recent years there has been an increasing awareness of the radiological impact of non-nuclear industries that extract and/or process ores and minerals containing naturally occurring radioactive material (NORM). These industrial activities may result in significant radioactive contamination of (by-) products, wastes and plant installations. In this study, scale samples were collected from a decommissioned phosphoric acid processing plant. To determine the nature and concentration of NORM retained in pipe-work and associated process plant, four main areas of the site were investigated: (1) the 'Green Acid Plant', where crude acid was concentrated; (2) the green acid storage tanks; (3) the Purified White Acid (PWA) plant, where inorganic impurities were removed; and (4) the solid waste, disposed of on-site as landfill. The scale samples predominantly comprise the following: fluorides (e.g. ralstonite); calcium sulphate (e.g. gypsum); and an assemblage of mixed fluorides and phosphates (e.g. iron fluoride hydrate, calcium phosphate), respectively. The radioactive inventory is dominated by 238U and its decay chain products, and significant fractionation along the series occurs. Compared to the feedstock ore, elevated concentrations (< or =8.8 Bq/g) of 238U were found to be retained in installations where the process stream was rich in fluorides and phosphates. In addition, enriched levels (< or =11 Bq/g) of 226Ra were found in association with precipitates of calcium sulphate. Water extraction tests indicate that many of the scales and waste contain significantly soluble materials and readily release radioactivity into solution.     

Evaluation of heavy metal acute toxicity and bioaccumulation in soil ciliated protozoa

Laboratory toxicity tests, using ciliated protozoa, are scarce and they have been carried out usually with freshwater species. In this study, we have analysed the acute cytotoxicity of Cd, Zn and Cu in five different strains of very common soil ciliate species (Colpoda steinii, Colpoda inflata and Cyrtolophosis elongata), which were isolated from very different soil samples (polluted or not with heavy metals). Soil ciliates are quite resistant to heavy metals pollution with regard to ciliates from other habitats. The toxicity sequence was Cd>Cu>Zn. Results from Cd+Zn mixtures indicated that Cd cytotoxicity decreases in the presence of low or moderate Zn concentrations. A broad heavy metal resistance level diversity exists among isolates of colpodid ciliates and it is seen to be a genetic feature rather than a habitat dependence. Bioaccumulation is seen to be the main mechanism involved in the metal resistance, except for Cu. For the first time in ciliates, a fluorescent method has been applied to detect Zn intracellular deposits. This methodology might be an useful tool for monitoring heavy metal pollution in soils.     

Assessment of state-of-the-art models for predicting the remobilisation of radionuclides following the flooding of heavily contaminated areas: the case of Pripyat River floodplain

The performances of models are assessed to predict the wash-off of radionuclides from contaminated flooded areas. This process should be accounted for in the proper management of the aftermath of a nuclear accident. The contamination of the Pripyat River water following the inundation of a floodplain heavily contaminated by (90)Sr and (137)Cs of Chernobyl origin is used as the basis for modelling. The available experimental evidence demonstrated that remobilisation of radiostrontium is an important process implying a significant secondary radioactive load of water flowing over the contaminated floodplain. On the contrary, there is no empirical evidence of a similar behaviour for radiocaesium. In general, state-of-the-art models properly predicted the remobilisation of strontium, whereas they significantly overestimated radiocaesium concentrations in water. The necessary model improvements for a more accurate prediction of radiocaesium contamination levels include a reassessment of the values of the model parameters controlling the remobilisation process.     

The application of phosphogypsum in agriculture and the radiological impact

Radium-226 in phosphogypsum produced in a phosphate industry, SICNG operating at Thessaloniki, Northern Greece since May 1966, varied from 261 to 688 Bq kg(-1) (mean value 508 Bq kg(-1)). This radionuclide in soil tilled with phosphogypsum used for agricultural purposes varied from 50 to 479 Bq kg(-1) (average 205 Bq kg(-1)), while in the regular soil of cultivated fields it varied from 37 to 54 Bq kg(-1) (average 48 Bq kg(-1)). Radium-226 in rice originated from cultivated fields tilled with phosphogypsum or not varied from 0.36 to 1.98 Bq kg(-1) (average 1.53 Bq kg(-1)) with the higher values observed in samples originated from cultivated fields tilled with phosphogypsum. Radium-226 transfer factors, TF, from soil tilled with phosphogypsum to plants for the case of rice varied from 6.5 x 10(-3) to 2.0 x 10(-2) (geometric mean: 1.1 x 10(-2)). A mean (226)Ra content in rice 1.53 Bq kg(-1) results in a daily intake of (226)Ra by humans in Greece 0.0084 Bq day(-1) leading to an annual effective dose for adults 0.86 microSv y(-1) which is much less in contributing to the average exposure to natural radiation sources (2.4 mSv y(-1)) and particularly to the part due to ingestion (0.29 mSv y(-1)). It is necessary to continuously control (monitoring) (226)Ra in phosphogypsum before any use for agricultural purposes.