Obsolete pesticide storage sites and their POP release into the environment—an Armenian case study

Organochlorinated pesticides were widely applied in Armenia until the 1980s, like in all former Soviet Union republics. Subsequently, the problem of areas contaminated by organochlorinated pesticides emerged. Environmental, waste and food samples at one pesticide burial site (Nubarashen) and three former pesticide storage sites (Jrarat, Echmiadzin and Masis) were taken and analysed on the content of organochlorinated pesticides, polychlorinated dibenzo-p-dioxins and furans and dioxin-like polychlorinated biphenyls. Gradient sampling and diffusivity-based calculations provided information on the contamination release from the hot spots on a local scale. A risk analysis based on samples of locally produced food items characterised the impact of storage sites on the health of nearby residents. All four sites were found to be seriously contaminated. High pesticide levels and soil and air contamination gradients of several orders of magnitude were confirmed outside the fence of the Nubarashen burial site, confirming pesticide release. A storage in Jrarat, which was completely demolished in 1996 and contained numerous damaged bags with pure pesticides until 2011, was found to have polluted surrounding soils by wind dispersion of pesticide powders and air by significant evaporation of lindane and β-endosulfan during this period. Dichlorodiphenyltrichloroethane-contaminated eggs, sampled from hens roaming freely in the immediate surroundings of the Echmiadzin storage site, revealed a significant health risk for egg consumers above 1E-5. Although small in size and previously almost unknown to the public, storage sites like Echmiadzin, Masis and Jrarat were found to stock considerable amounts of obsolete pesticides and have a significant negative influence on the environment and human health. Multi-stakeholder cooperation proved to be successful in identifying such sites suspected to be significant sources of persistent organic pollutants.     

Time to death response in carabid beetles exposed to multiple stressors along a gradient of heavy metal pollution

We investigated the responses of invertebrates inhabiting polluted environments to multiple stressors. Carabid beetles (Pterostichus oblongopunctatus F.) were subjected to food deprivation and insecticide treatment (dimethoate) to resolve trends associated with a gradient of heavy metal pollution. Metal concentrations along the gradient of five sites ranged from approximately 150 to 10,500 mg/kg Zn, 136 to 2600 mg/kg Pb, and 0.84 to 81.9 mg/kg Cd. There was no difference in body mass along the pollution gradient. However, the beetles originating from the most contaminated sites were significantly less tolerant to food deprivation than beetles from the reference site. Median survival time was 120 h for the two most polluted sites, compared with 168 h at the reference site. Beetles from the two most polluted sites were also significantly more susceptible to dimethoate at 0.1 microgram active ingredient/beetle. Median survival times were 12 and 123 h for beetles from the two most polluted sites and 359 h for the reference site. Carabid beetles exposed to chronic pollution, therefore, exhibit elevated susceptibility to additional stressors.     

Budburst phenology of white birch in industrially polluted areas

Effects of environmental contamination on plant seasonal development have only rarely been properly documented. Monitoring of leaf growth in mountain birch, Betula pubescens subsp. czerepanovii, around a nickel-copper smelter at Monchegorsk hinted advanced budburst phenology in most polluted sites. However, under laboratory conditions budburst of birch twigs cut in late winter from trees naturally growing around three point polluters (nickel-copper smelter at Monchegorsk, aluminium factory at Kandalaksha, and iron pellet plant at Kostomuksha) showed no relationship with distance from the emission source. In a greenhouse experiment, budburst phenology of mountain birch seedlings grown in unpolluted soil did not depend on seedling origin (from heavily polluted vs. clean sites), whereas seedlings in metal-contaminated soil demonstrated delayed budburst. These results allow to attribute advanced budburst phenology of white birch in severely polluted sites to modified microclimate, rather than to pollution impact on plant physiology or genetics.     

Impact of metals on histopathology and expression of HSP 70 in different tissues of Milk fish (Chanos chanos) of Kaattuppalli Island, South East Coast, India

Histological and Immunohistochemical studies were carried out to document the possible impact of heavy metal contamination in different tissues of Chanos chanos. Heavy metals such as Cu, Pb, Zn, Cd, Mn and Fe were predominant in water, sediment and biota of Kaattuppalli Island and varied significantly between two different sites. Histological changes such as swelling of muscle fiber and break down of muscle bundles were noted in the muscle. Similarly gill filament cell proliferation, increase in intercellular spaces and primary and secondary lamellar epithelium were evident in gills. The hepatocytes showed damage of central vein and rupture of irregular hepatic plate with more number of vacuoles in the fish collected from polluted site compared to that from the less polluted site. The impact of pollution was also assessed in different tissues by immunohistochemistry using primary antibody (mouse monoclonal HSP70 antibody 1:2000) and secondary antibody (HRP conjugated antibody) for expression of stress protein. Immunostaining analysis showed expression of HSP70 with high intensity in the tissues of fish collected from polluted site compared to less polluted sites. Further, HSP70 positive cells were analyzed from six locations per fish tissue section. One-way analysis of variance (ANOVA) followed by least significant difference (LSD) was used to check if the expression was significant. Results indicate that the values are statistically significant at the two different sampling sites (P<0.05).     

Factors determining amounts of fluoride in woodlice Oniscus asellus and Porcellio scaber, litter and soil near an aluminium reduction plant

Amounts of fluoride were measured in whole woodlice Oniscus asellus and Porcellio scaber, together with associated soil and litter, from 17 sites near an aluminium reduction plant at Holyhead, Anglesey, in North Wales. There was a strong positive correlation between amounts of fluoride in woodlice, soil and litter in all comparisons (P<0.02). Highest and lowest fluoride concentrations in woodlice differed by a factor of >50. Where both woodlice species occurred together at the more polluted sites, fluoride levels in Oniscus asellus were generally twice as high as those found in Porcellio scaber. At any given site, amounts of environmental fluoride were determined partly by distance and direction from the pot-rooms of the plant (a function of prevailing winds), modified by the presence of trees which acted as collectors for gaseous and particulate fluoride.     

Studies on the progeny of rice plants grown at an unpolluted and polluted site

Oryza sativa L. cv. GR3 was grown near to a fertilizer plant and the growth of its seed progeny was evaluated at sites near to, and distant from, the fertilizer plant. The grain yield was reduced in plants grown at the polluted site, with reduced panicle length and increased sterility index. This decrease in grain yield was higher in the progeny plants than in the normal polluted plants. The polluted progeny grown at a control site showed a normal yield, but an increased sterility index. Accumulation of total sulphur and fluoride was higher in the leaves of polluted rice plants. It was evident that tolerance to air pollution was reduced in the progeny plants due to an additional dosage of sulphur and fluoride pollutants and to unfavourable climatic factors. Further, pollution effects were not carried over in progeny plants when grown in an unpolluted environment.     

Effects of dietary and gaseous fluoride on the aphid Aphis fabae

A large proportion of leaf fluoride consists of surface deposits and a sucking herbivore would be expected to take in a smaller load of fluoride in its food than a chewing herbivore. In these experiments, fluoride was applied aerially, through the leaves, and systemically, via the roots, to compare uptake by aphids and effects on their fecundity. Fluoride applied via roots was taken up by both the plants and the aphids, but at high treatment rates the aphids had much lower concentrations than the foliage. When the plants and aphids were fumigated with HF the aphids had much greater loads than the plant shoots, which was due to deposition of F on the insect surfaces. There were no effects of the treatments on aphid reproduction or development time. The aphids obtained some fluoride through their diet which suggests that fluoride is present in the phloem sap, previously thought to be of minor importance.     

Sediment-associated aliphatic and aromatic hydrocarbons in coastal British Columbia, Canada: concentrations, composition, and associated risks to protected sea otters

Sediment-associated hydrocarbons can pose a risk to wildlife that rely on benthic marine food webs. We measured hydrocarbons in sediments from the habitat of protected sea otters in coastal British Columbia, Canada. Alkane concentrations were dominated by higher odd-chain n-alkanes at all sites, indicating terrestrial plant inputs. While remote sites were dominated by petrogenic polycyclic aromatic hydrocarbons (PAHs), small harbour sites within sea otter habitat and sites from an urban reference area reflected weathered petroleum and biomass and fossil fuel combustion. The partitioning of hydrocarbons between sediments and adjacent food webs provides an important exposure route for sea otters, as they consume ∼25% of their body weight per day in benthic invertebrates. Thus, exceedences of PAH sediment quality guidelines designed to protect aquatic biota at 20% of the sites in sea otter habitat suggest that sea otters are vulnerable to hydrocarbon contamination even in the absence of catastrophic oil spills.     

Microbenthic community structure and trophic status of sediments in the Mar Piccolo of Taranto (Mediterranean,Ionian Sea)

This study aimed to assess the benthic ecosystem trophic status in a heavily polluted marine area and the response of the microbenthic community to multiple and diffuse anthropogenic impacts, integrating information coming from the active and resting (plankton’s cysts) components of microbenthos. Two sampling campaigns were carried out in the period 2013–2014 and four sampling sites at different levels of industrial contamination were chosen within the first and second inlet of the Mar Piccolo of Taranto. The chemical contamination affected to a higher extent the active microbenthos than the resting one. In the central part of the first inlet, characterised by more marine features, thrives a very rich and biodiverse microbenthic community. In contrast, at the polluted site near the military navy arsenal, extremely low densities (9576?±?1732 cells cm^?3) were observed for active microbenthos, but not for the resting community. Here, the high level of contamination selected for tychopelagic diatom species, i.e., thriving just above the surface sediments, while the other life forms died or moved away. Following the adoption of a 10 μm mesh, for the first time, resting spores produced by small diatoms of the genus Chaetoceros were found. Our results further indicate that although the Mar Piccolo is very shallow, the benthic system is scarcely productive, likely as a consequence of the accumulated contaminants in the surface sediments that probably interfere with the proper functioning of the benthic ecosystem.     

Fish community responses to pulp and paper mill effluents at the southern Lake Saimaa, Finland.

The fish community in sublittoral and profundal waters, at stony shores, and densities of vendace larvae were studied in the southern Lake Saimaa, Finland. The objective was to investigate the possible recovery of fish populations after modernizations at the pulp and paper mills discharging into the lake. Sublittoral and profundal waters were studied by gill net trial fishings, stony shores by electrofishing, and vendace larvae by beach seine. The research area was divided in a polluted (0.5-4.0% effluent), an intermediate (0.1-0.5%) and a 'clean' reference area. The fish community in sublittoral and profundal waters in the lake was dominated (> 60%) by perch and roach. Relative abundance of fish was highest in the polluted area, and lowest in the reference area. The number of species caught was similar among areas. The abundance of bleak and ruffe was highest in the polluted area, while the abundance of vendace and whitefish was highest in the intermediate and reference area. The fish fauna of stony shores in the lake was dominated by bullhead, stone loach and minnow, densities were lowest at polluted shores and highest in the intermediate area. Minnow, apparently a more sensitive species to pulp mill effluents, were not caught at the most polluted shores. The catch of vendace larvae was similar among areas, larvae were also caught in the vicinity of the mills. Compared with before the modernization at the mills, the relative abundance of perch in the polluted area was increased, ruffe decreased, while populations of whitefish and vendace showed signs of recovery. These changes may be explained by the reduced nutrient load and toxicicity of pulp mill effluents. At present, the fish community in the polluted area can be considered typical for a moderate eutrophication.     

Do wood mice (Apodemus sylvaticus L.) use food selection as a means to reduce heavy metal intake?

Food preference of wood mice from two with heavy metals polluted sites and two unpolluted sites was tested under laboratory and field conditions with two-way choice experiments. In the laboratory, wood mice preferred to eat acorns from unpolluted sites over acorns from polluted sites. Previous experience with polluted food had no influence on food choice. Preference was negatively related to acorn metal content. Furthermore, the nutrient content of the acorn endosperm was consistently lower in polluted sites. We therefore conclude that wood mice used absolute metal concentration in the acorn, nutrient content, or both as a food selection cue. The results of the laboratory experiment could not be confirmed under field conditions. We hypothesized that search time constraints due to the presence of predators, competitors and/or other stress factors in the field have prevented the mice to forage selectively.     

Ecological risk assessment of arsenic and metals in sediments of coastal areas of northern Bohai and Yellow Seas, China

Distributions of arsenic and metals in surface sediments collected from the coastal and estuarine areas of the northern Bohai and Yellow Seas, China, were investigated. An ecological risk assessment of arsenic and metals in the sediments was evaluated by three approaches: the Sediment Quality Guidelines (SQGs) of the United States Environmental Protection Agency (USEPA), the degree of contamination, and two sets of SQGs indices. Sediments from the estuaries of the Wuli and Yalu Rivers contained some of the greatest concentrations of arsenic, cadmium, copper, mercury, lead, and zinc. Median concentrations of cadmium and mean concentrations of lead and zinc were greater than background concentrations determined for the areas. All sediments were considered to be heavily polluted by arsenic, but moderately polluted by chromium, lead, and cadmium. Current concentrations of arsenic and metals are unlikely to be acutely toxic, but chronic exposures would be expected to cause adverse effects on benthic invertebrates at 31.4% of the sites.     

Nationwide monitoring of polychlorinated biphenyls and organochlorine pesticides in sediments from coastal environment of Korea

To assess the organochlorine contamination in the Korean marine environment, a nationwide monitoring study was conducted. A total of 138 surface sediments, covering the whole Korean coast, were collected and analyzed. Organochlorine compounds (OCs) were widely distributed in the Korean coastal environment, with PCB and DDT contamination being particularly prevalent. The overall concentrations of PCBs, DDTs, HCHs, CHLs, and HCB in surface sediments were in the range of 0.088-199ngg(-1) (median value: 1.56ngg(-1)), 0.006-135ngg(-1) (0.68ngg(-1)), not detected (ND)-5.46ngg(-1) (0.32ngg(-1)), ND-3.26ngg(-1) (0.14ngg(-1)), and ND-2.59ngg(-1) (0.05ngg(-1)), respectively. The southeastern coast was found to be highly contaminated. Overall contamination status of Korean coastal sediments with regard to OCs is lower than that of USA. With the exception of highly industrialized sites, Korean coastal areas in general showed similar OC concentrations to those of other Asian countries. There was a significant correlation between distributions of most organochlorine contaminants with each other. OC contamination is closely related to shipping and industrial activities. Of the 7 sites categorized as highly polluted, 4 are in a harbor zone. Adverse effects to benthic communities are expected at the levels of OC contamination observed from harbor and industrial areas.     

Assimilation efficiencies of Cd and Zn in the common carp (Cyprinus carpio): effects of metal concentration, temperature and prey type

The impact of several factors on the assimilation efficiency (AE) of Cd and Zn from food in the common carp (Cyprinus carpio) was studied. Tested prey species were midge larvae (Chironomus riparius), zebra mussels (Dreissena polymorpha) and oligochaetes (Tubifex tubifex). The Cd load of the larvae did not affect the Cd AE in the carp. The Zn AE however, was negatively related to the Zn load of the prey. Food quantity and starvation of the carp did not significantly affect the Cd AE. For Zn, a significant decrease in AE was found when carp were fed ad libitum. Decreasing the temperature from 25 degrees C to 15 degrees C did not influence the Cd AE, while for Zn a significant decrease of the AE was measured. Carp assimilated Cd from both zebra mussels and oligochaetes with a significantly lower efficiency in comparison to the midge larvae, although Zn AEs was prey independent.     

Relationships between metal concentrations in great tit nestlings and their environment and food

Metal concentrations (Ag, As, Cd, Cu, Hg, Ni, Pb, Zn) were determined in the feathers and excreta of nestling great tits (Parus major), in their main invertebrate prey (Lepidoptera larvae) and in vegetation samples, all collected from four sites along a pollution gradient. Metal contamination in vegetation samples increased significantly towards the pollution source. The Ag, As, Hg, Ni and Pb concentrations in food samples were significantly higher at the site closest to the pollution source compared to the other three sites. Great tit nestlings from the site closest to the pollution source had significantly higher concentrations of Ag, As, Hg and Pb in their excreta than did nestlings at the other three sites. For five metals (Ag, As, Cu, Ni and Pb), we found concentrations in caterpillars to be significantly positively correlated with vegetation samples. We also found clear significant positive correlations between excreta and caterpillars for Ag, As, Hg and Pb and between feathers and caterpillars for As and Pb. Our data suggest that excreta are a good monitor for the presence and concentrations of non-essential metals in the food and the environment of passerine birds.     

Root versus canopy uptake of heavy metals by birch in an industrially polluted area: contrasting behaviour of nickel and copper

We investigated root versus canopy uptake of nickel and copper by mountain birch, Betula pubescens subsp. czerepanovi, close to a nickel-copper smelter on the Kola Peninsula, northwest Russia. To distinguish between aerial contamination of leaf surfaces by dust particles and root-derived contamination of leaves by soluble metals, we transplanted seedlings from a control site to clean and metal-contaminated soils and exposed these seedlings both in clean and polluted sites. Patterns of leaf surface contamination and root uptake were similar for nickel and copper; however, nickel but not copper was effectively translocated from roots to shoots and leaves. The majority (80-95%) of nickel and copper found in birch foliage in the heavily contaminated site was due to deposition of dust particles on leaf surfaces; 32-40% of foliar nickel and 9-19% of foliar copper were in water soluble forms. Washing of fresh leaves removed only a minor part of surface contaminants; boiling of unwashed leaves in distilled water for 15 min removed >90% of soluble nickel and copper.     

Reduced survival and body size in the terrestrial isopod Porcellio scaber from a metal-polluted environment

Terrestrial isopods (woodlice) may show trade-offs in life history parameters when exposed to toxins. We have shown previously [Jones and Hopkin (1996) Functional Ecology 10, 741-750] that woodlice which survive to reproduce in sites heavily polluted with metals from an industrial smelting works do not alter their reproductive allocation. This study investigates whether there are differences in the survival and body size of Porcellio scaber from these same populations. Specimens were collected from eight sites at different distances from the Avonmouth smelter, UK. The sites represented a gradient of concentrations of Zn, Cd, Pb and Cu in the woodlice, from background levels to a grossly contaminated sites close to the smelter. In laboratory trials, the number of days survived by starved males showed a significant decline with increased concentrations of Zn in those animals. The maximum size of both sexes declined significantly from the least to the most polluted sites. The most polluted sites had significantly fewer large animals. The cost of detoxifying assimilated metals appears to be reduced energy reserves and smaller body size.     

ELISA detection of multixenobiotic resistance transporter induction in indigenous freshwater Chironomidae larvae (Diptera): A biomarker calibration step for in situ monitoring of xenobiotic exposure

A new simple and sensitive method to distinguish chemically polluted from unpolluted situations in freshwater ecosystems is reported. For this purpose, Chironomus gr thumni larvae were collected from a polluted urban river downstream a sewage treatment plant. For the first time, ELISA assay was used to semi-quantify the multixenobiotic resistance transporters (MXR) in these small pertinent bioindicators. The use of samples immediately fixed in the field gives a delay to isolate larvae and allows multi-sampling along a longitudinal transect in a river at a given time. Results exhibit an induction of MXR proteins in larvae from the polluted river and a deinduction in larvae maintained 11days in unpolluted water. They show new evidences to use midge larvae in biomonitoring environmental programs. They answer to first biomarker calibration steps for the ongoing development of MXR transporters as a detection tool of xenobiotic impacts on bioindicator invertebrates in their freshwater habitats.     

Polychlorinated naphthalenes in sediments from the Venice and Orbetello lagoons, Italy

The purpose of this study was to evaluate the contamination caused by polychlorinated naphthalenes in two polluted Mediterranean lagoons. Surface sediment samples from Venice and Orbetello lagoons were analysed using HRGC-HRMS. The levels of the sum of mono- to octa-CN ranged from 0.03 to 1.51 ng/g. Differences in PCN levels were observed as a function of the sampling site, with levels at the industrial sites exceeding those at the control sites. Although the PCN patterns and profiles resembled one another in different sediment samples, they differed considerably when compared with those in the technical PCN formulation Halowax 1014.     

Distribution, origin and fate of chromium in soils in Guanajuato, Mexico

Total, hexavalent and trivalent chromium were determined in surface and 30-cm depth soil samples from a highly chromium-polluted area in Guanajuato state, central México. Four samples were also analyzed by a sequential extraction procedure. Nearly 0.9 km(2) out of the 8 km(2) area sampled was polluted with chromium, at concentrations up to 12960 mg kg(-1), mostly as Cr(III). Concentrations of Cr(VI) were lower than 0.5 mg kg(-1) in most sampled points, with the exception of one, where the concentration was found to be 65.14 mg kg(-1). Chromiumcontaining dust from a chromate factory accounted for most of the contamination. The highest concentrations of hexavalent chromium in soil, were in the bottom sediments of an abandoned water reservoir used to store polluted water from a well, before use of the water in the factory process. Tannery wastes, dust from a sanitary landfill of chromate compounds and the transport of chromium products are the sources of chromium at other sites. Chromium is fixed preferentially in the hydrous Fe and Mn oxides in the more polluted soils. Less polluted soils have a high proportion of chromium associated with the sulfide and organic fraction. Cr(III) is retained preferentially in the superficial soil layer. Variations in the physical characteristics of the soil, relative abundance of the various soil components and characteristics of the contaminant source, give rise to differences in chromium soil concentrations with depth.