Organotin compounds in surface sediments from seaports on the Gulf of Gda??sk (southern Baltic coast)

Sediment samples were collected in two Polish ports of international significance--the Port of Gdańsk and the Port of Gdynia (Gulf of Gdańsk, Baltic Sea)--in order to assess their butyltin and phenyltin contamination; this was done in 2008, just after the total ban on using harmful organotins in antifouling paints on ships came into force. Altogether, 21 sampling stations were chosen to present a diversity of port sites: from port canals and shipyards to anchorages and dumping sites. The organic carbon content and grain size of all the sediment samples were determined, and some environmental parameters (oxygen content, salinity) were measured as well. Total concentrations of butyltin compounds in sediment samples were very different and ranged between 1 and 18,520 ng Sn g(-1) d.w. Phenyltin contents were distinctly lower and ranged from below the limit of detection (most samples) to 660 ng Sn g(-1) d.w. The highest concentrations of organotins were found in the shipyards, the maximum total organotin content (19,180 ng Sn g(-1) d.w.) being found in the Gdańsk Ship Repair Yard 'Remontowa'. Butyltin degradation indices indicate a recent tributyltin input into the port sediments. The results obtained from this work prove that the international ban on using organotins may not be enough to protect the marine environment. It is necessary to monitor organotin contamination in ports and establish concentration limits of these compounds for the disposal of dredged material at sea.     

Toxicity assessment of sediments associated with the wreck of s/s Stuttgart in the Gulf of Gdańsk (Poland)

The paper presents the results of toxicity determinations carried out on sediment samples collected in the vicinity of the wreck of the German s/s Stuttgart (the southern part of the Gulf of Gdańsk, off the Polish coast) in relation to the determination of polycyclic aromatic hydrocarbons (PAHs). The toxicity of surface and core sediment samples was assessed using two biotest organisms-the bioluminescent bacteria Vibrio fischeri and the ostracod Heterocypris incongruens. PAH levels in these samples were determined by GC-MS. The surface sediments collected at W2 (ca. 34 m north of the shipwreck) and W4 (ca. 415 m north-east of the wreck) as well as the core sediments collected at WR3 (ca. 400 m north-east of the wreck) were the most heavily polluted with substances toxic to the biotest organisms. The chronic and acute toxicities in the case of most of the surface sediment samples studied are correlated. This may suggest that not only hydrophobic chemicals (like PAHs from fuel residues) but also more polar chemicals (resulting from the conversion of aromatic hydrocarbons) are responsible for the toxicity levels found. There is a clear dependence between the levels of chronic toxicity and PAH concentrations in the core sediment samples. In addition, a simultaneous decrease in the PAH content and chronic toxicity was noted in all the core sediment samples at depths below 80 cm.     

Historical changes of sediments and mollusk assemblages in the Gulf of Batabanó (Caribbean Sea) in the twentieth century

The first paleoecological reconstruction of the biogeochemical conditions of the Gulf of Batabanó, Caribbean Sea was performed from (210)Pb-dated sediment cores. Depth profiles of 20 major elements and trace metals, organic compounds, grain size, and mollusk assemblage composition were determined from 9 stations encompassing unconsolidated sediments in the gulf. Spatial heterogeneity was evident for the geochemistry of sediments and for the mollusk assemblage composition. Our reconstruction indicates that pollution is not a critical threat to the ecosystem, although a slight historical increase of lead enrichment factor was detected probably due to long-range atmospheric fallout. Mollusk assemblages were composed by 168 species belonging to 59 families and no temporal trends in the species diversity or assemblage composition were detected, suggesting no depletion of diversity or habitat loss. Other signals of habitat loss such as changes in organic budget or increase of fine sediment fraction were absent or weak. Nitrogen retained in sediments changed by <1% in the century, indicating no historical events of eutrophication or oligotrophication in the gulf. Historical decrease of fine sediment fraction in the eastern sector would be linked to modifications in sedimentation rate, land use, and/or particle transport from the shelf border; this also suggests that both sectors have different sedimentary dynamics. Although, on theoretical grounds, historical fishery may have caused deleterious ecosystem effects by overexploitation of spiny lobster stocks, no evidence of habitat degradation or loss, caused by fisheries, could be detected.     

Linear alkylbenzene sulfonate (LAS) in water of Lake Dianchi—spatial and seasonal variation, and kinetics of biodegradation

Agroforesty systems, which are recommended as a management option to lower the shallow groundwater level and to reuse saline subsurface drainage waters from the tile-drained croplands in the drainage-impacted areas of Jan Joaquin Valley of California, have resulted in excessive boron buildup in the soil root zone. To assess the efficacy of the long-term impacts of soil boron buildup in agroforesty systems, a mathematical model was developed to simulate non-conservative boron transport. The developed dynamic two-dimensional finite element model simulates water flow and boron transport in saturated–unsaturated soil system, including boron sorption and boron uptake by root-water extraction processes. The simulation of two different observed field data sets by the developed model is satisfactory, with mean absolute error of 1.5 mg/L and relative error of 6.5%. Application of the model to three different soils shows that boron adsorption is higher in silt loam soil than that in sandy loam and clay loam soils. This result agrees with the laboratory experimental observations. The results of the sensitivity analysis indicate that boron uptake by root-water extraction process influences the boron concentration distribution along the root zone. Also, absorption coefficient and maximum adsorptive capacity of a soil for boron are found to be sensitive parameters.     

Use of metallothioneins as biomarkers for environmental quality assessment in the Gulf of Gabès (Tunisia)

Detection and assessment of the impact of pollution on biological resources imply increasing research on early-warning markers such as metallothioneins (MTs) in metal exposure. In this paper, we have collated published information on the use of metallothioneins and metallothionein-like proteins (MTLPs) as biomarkers for environmental quality assessment in the Gulf of Gabès. In this area, some species of fish and bivalve were used as bioindicators of pollution. In these species, an induction of MTs/MTLPs by the essential metals such as Cu and Zn and the non-essential metals such as Cd was observed by different authors who suggest the potential use of these proteins as biomarkers. However, MT concentrations can be influenced by many biotic (sex, maturity stages, and tissues) and abiotic factors (temperature, salinity, and pH). This is essentially the case in field studies where many parameters can randomly affect MT levels, so the endogeneous regulation of MTs must be considered before using MTs as an indicator of heavy metal exposure. Moreover, the use of biomarker cannot be examined independently of the evaluation of techniques that enable its quantification. Therefore, the approach to the use of MTs/MTLP as biomarkers of exposure for an assessment of the physiological status of aquatic organisms is discussed in this paper.     

Trace metal (Cd,Cu, Pb,Zn) fractionation in urban-industrial soils of Ust-Kamenogorsk (Oskemen), Kazakhstan—implications for the assessment of environmental quality

Ust-Kamenogorsk is one of the largest cities and industrial centers in Kazakhstan. Non-ferrous metallurgy (Zn–Pb smelter) has acted as a predominating industrial branch in the city since late 1940s. The industrial plants are situated directly adjacent to the residential area of the city which creates grievous ecotoxicological hazard. In the present paper, we aimed at assessing the trace metal pollution of top soils in Ust-Kamenogorsk and its potential threats to the local population. The top soils were sampled at 10 sites throughout the city center. We determined the physical and chemical properties of soils as well as the contents of Cd, Cu, Pb, and Zn. In addition, the soil samples were subjected to a five-step sequential extraction to ascertain the fractionation of trace metals. On this basis, we calculated the geoaccumulation index (I_geo) and pollution load index (PLI) and assessed bioavailability of the elements. From our data, it emerged that the soils displayed a strong polymetallic pollution. PLI was as high as 33.4. Throughout the city, the trace metal contents exceeded the geochemical background and allowable values for residential, recreational, and institutional areas. The I_geo obtained were 3.7–6.5 for Cd, 1.5–4.7 for Cu, 2.8–5.7 for Pb, and 2.6–4.6 for Zn. The soils in Ust-Kamenogorsk displayed extremely high contamination with Cd, moderate to strong contamination with Pb and Zn, and low to moderate contamination with Cu. Cd and Pb were found to be the most bioavailable elements. The mobility of trace metals in the soils changed in the order Cd > Pb > Zn > Cu.     

Spatial distribution of major and trace elements in the water of Swarzędzkie Lake (Poland)

In order to characterize the contamination of the Swarzedzkie Lake and generate elemental distribution patterns 18 elements have been determined in samples of water, taken just above the bottom sediments. Analyses were carried out using two instrumental techniques - ICP-OES and ICP-MS. Two main sources of contamination were identified - diffuse pollution from agriculture and stormwater from the town. Three separate groups of elements were distinguished using cluster analysis and two groups using principal component analysis. These three groups are characterized as geogenic elements (Ag, As, Mg and Sb), elements supplied by the agricultural catchment (Ca, Mn, Sr, Na, K and Al) and elements originated from the urban contamination (Ni, Cr, Cu, Fe, V, Ba, Zn and Pb). PCA differentiated the above group of urban elements from the rest, originated from diffuse sources, with exception of alluminium, which was situated between two distinguished groups.     

Spatial and temporal distribution of tributyltin (TBT) in seawater, sediments and bivalves from coastal areas of Korea during 2001–2005

Tributyltin (TBT) concentrations were determined in seawater, sediments and bivalve samples collected from Korean coastal areas during 2001-2005, to investigate the levels and temporal variation in TBT contamination in relation to the timing of the imposition of regulations on TBT use in Korea. TBT concentrations ranged from <5.0 to 164 ng/L in seawater, from <7.0 to 9,576 ng/g dry weight in sediments, and from <7.0 to 6,296 ng/g dry weight in bivalves. The highest concentrations of TBT were found at locations close to intensive shipping traffic and industrial complexes, and the contamination at some hot spot areas was high enough to cause harmful effects on marine organisms. TBT concentrations and their occurrence in Korean coastal waters have been decreasing annually. In particular, TBT concentrations in seawater have dramatically decreased. This result is consistent with regulations and bans on the use of TBT in Korea.     

Association of spinal deformities with heavy metal bioaccumulation in natural populations of grass goby, Zosterisessor ophiocephalus Pallas, 1811 from the Gulf of Gabès (Tunisia)

The present study illustrates an analysis of spinal deformities associated with metal accumulation in natural populations of Zosterisessor ophiocephalus derived from polluted (S1) and unpolluted (S2) areas in the Gulf of Gabès in Tunisia. Three basic types of spinal deformities were detected: kyphosis, scoliosis and lordosis. These basic deformities frequently co-occur. Spinal deformities were observed in 10.72% of the total examined fish (n = 494). Deformed fish were 3.85 times more frequent in S1 than in S2. In both sexes, the highest occurrence of deformities was observed in the 111-120 mm class decreasing thereafter with fish length. Hepatic concentrations of cadmium (Cd), copper (Cu) and zinc (Zn) were significantly higher in Z. ophiocephalus from S1 than those from S2. Comparisons between fish in each site showed that liver concentrations of Cd and Zn were significantly higher in deformed fish than in normal fish. The relationship between metals accumulation and observed spinal deformities as well as the suitability of this kind of studies for environmental monitoring are discussed.     

Levels and distribution of persistent organochlorine pesticide residues in water and sediments of Gomti River (India)—a tributary of the Ganges River

This study reports the concentration levels and distribution pattern of the persistent organochlorine pesticide (OCPs) residues in the water and bed-sediments of the Gomti River collected seasonally over a period of 2 years. The water and bed-sediment samples were collected from eight different sites and analyzed for aldrin, dieldrin, endrin, HCB, HCH isomers, DDT isomers/metabolites, endosulfan isomers (alpha and beta), endosulfan sulfate, heptachlor and its metabolites, alpha-chlordane, gamma-chlordane and methoxychlor. In the river water and sediments SigmaOCPs residues ranged between 2.16 and 567.49 ng l(-1) and 0.92 and 813.59 ng g(-1), respectively. The results, further, suggested that source of DDT contamination is from the aged and weathered agricultural soils with signature of recently used DDT in the river catchments. To assess any adverse effect of OCPs contamination on river's biological component, the threshold effect level (TEL) was used. The results revealed that bed-sediments of the Gomti River are contaminated with lindane, endrin, heptachlor epoxides and DDT, particularly at site-4 and may contribute to sediment toxicity in the freshwater ecosystem of the river.     

Short-term variability of water quality and its implications on phytoplankton production in a tropical estuary (Cochin backwaters—India)

Changes in the phytoplankton biomass (chlorophyll a), production rate, and species composition were studied over two seasons using the time series measurements in the northern limb of the Cochin estuary in relation to the prevailing hydrological conditions. The present study showed the significant seasonal variation in water temperature (F = 69.4, P < 0.01), salinity (F = 341.93, P < 0.01), dissolved inorganic phosphorous (F = 17.71, P < 0.01), and silica (F = 898.1, P < 0.01) compared to nitrogen (F = 1.646, P > 0.05). The uneven input of ammonia (3.4–224.8 μM) from upstream (Periyar River) leads to the inconsistency in the N/P ratio (range 6.8–262). A distinct seasonality was observed in Si/N (F = 382.9, P < 0.01) and Si/P (F = 290.3, P < 0.01) ratios compared to the N/P ratio (F = 1.646, P > 0.05). The substantial increase in chlorophyll a (average, 34.8 ± 10 mg m^???3) and primary production (average, 1,304 ± 694 mg C m^???3 day^???1) indicated the mesotrophic condition of the study area during the premonsoon (PRM) and it was attributed to the large increase in the population of nanoplankton (size < 20 μ ) such as Skeletonema costatum, Thalassiosira subtilis, Nitzschia closterium, and Navicula directa. In contrast, during the post monsoon (PM), low chlorophyll a concentration (average, 9.3 ± 9.2 mg m^???3) and primary production (average, 124 ± 219 mg C m^???3 day^???1) showed heterotrophic condition. It can be stated that favorable environmental conditions (optimum nutrients and light intensity) prevailing during the PRM have enhanced the abundance of the nanoplankton community in the estuary, whereas during the PM, the light limitation due to high turbidity can reduce the nanoplankton growth and abundance, even though high nutrient level exists.     

Heavy metal concentration in deepwater rose shrimp species (Parapenaeus longirostris,Lucas, 1846) collected from the Marmara Sea Coast in Tekirdağ

Zn, Cd, Cr, Hg, As (total), Cu, Pb, and Ni levels of the deepwater rose shrimp (Parapenaeus longirostris, Lucas 1846), which were collected from the Tekirda? coast of the Marmara Sea, were evaluated. The Marmara Sea is the recipient of discharges from both land-based sources and the Black Sea Bosphorus stream. There are large numbers of anthropogenic activities in the coastal region of the northern Marmara Sea that include urban effluent, discharges from touristic resorts, agricultural runoff, fishing, and transportation. Heavy metal contamination of water resources may cause critical health problems for the people living around these water bodies. In deepwater rose shrimp (P. longirostris), the highest concentration level detected for Zn was 22.4?±?24.4 mg/kg in winter 2012, Cd 0.106?±?0.01 mg/kg in summer 2012, Cr 0.77?±?0.05 mg/kg in winter 2012, Hg 0.18?±?0.04 mg/kg in summer 2011, As 9.93?±?1.4 mg/kg in spring 2012, Cu 25.48?±?0.3 mg/kg in winter 2012, Pb 2.12?±?0.8 mg/kg in spring, and Ni 19.25?±?7.1 mg/kg in spring. The values of heavy metal analysis were compared to both the Turkish Food Codex (TFC) limits and international standards for human consumption. The Pb, As, and Cu levels were found to be higher than the maximum allowable limits.     

Trace elements (Cu,Zn, and Hg) and δ<Superscript>13</Superscript>C/δ<Superscript>15</Superscript>N in seabird subfossils from three islands of the South China Sea and its implications

Seabird subfossils were collected on three islands of the Xisha Archipelago, South China Sea. Via elemental analysis, we identified that bird guano was a significant source for heavy metals Cu, Zn, and Hg. Cu and Zn levels in these guano samples are comparable to their levels in wildbird feces, but guano Hg was lower than previously reported. Trophic positions significantly impacted transfer efficiency of heavy metals by seabirds. Despite of a common source, trace elements, as well as stable isotopes (i.e., guano δ¹³C and collagen δ¹⁵N), showed island-specific characteristics. Bird subfossils on larger island had relatively greater metal concentrations and revealed higher trophic positions. Partition of element and isotope levels among the islands suggested that transfer efficacy of seabirds on different islands was different, and bird species were probably unevenly distributed among the islets. Island area is possibly a driving factor for distributions of seabird species.     

Temporal distribution of cyanobacteria in the coast of a shallow temperate estuary (Río de la Plata): some implications for its monitoring

The aim of this study was to analyze the temporal distribution of phytoplanktonic cyanobacteria in a site located in the freshwater tidal zone near the extraction point for the drinking water supply. Samples were taken considering three timescales as follows: hours, days, and weeks, during the period of highest development of cyanobacteria. The phytoplankton density, microcystin concentration (LR, RR, YR), and chlorophyll-a were related to meteorological variables (wind and temperature), tidal high, and physical-chemical variables (nutrients, pH, conductivity, light penetration). The results obtained in this study showed that the variables that primarily modulate the temporal distribution of cyanobacteria were temperature, pH, light penetration, conductivity, and nutrients (particularly NO₃ ^? and NH₄ ⁺), while the winds and tide had a secondary effect, only evidenced at an hourly scale. Therefore, this timescale would be the most suitable for monitoring cyanobacterial populations, when the amount of cyanobacterial cells exceeds the alert I level proposed by the World Health Organization. This recommendation is particularly important for the water intake zones in Río de la Plata, which are vulnerable to the damage generated by cyanobacteria on the water quality.     

Presence, distribution, and origins of polycyclic aromatic hydrocarbons (PAHs) in sediments from Bahía Blanca estuary, Argentina

This paper is the first comprehensive survey of polycyclic aromatic hydrocarbons (PAHs) in coastal sediments in Bahia Blanca, Argentina, and provides useful information on their levels of concentration, composition, and sources of these pollutants. The total concentrations of PAHs ranged from 15 to 10,260 ng g^???1. The highest contents (mean 3,315 ng g^???1) of total PAHs in marine sediments were found in the inner channels of the estuary, while the lower ones (204 ng g^???1) belong to samples collected far away from contamination sources. The global average recorded in this study (1,500 ng g^???1) indicates that the studied area lies within the referenced category of industrialized coastal zones under chronic pollution. The diagenetic PAH contribution was found to be negligible at all sampled locations; however, the calculation of molecular ratios determined an overimposition of pyrolitic PAHs over the petrogenic input. Further, the use of principal components analysis (PCA) clearly separated ring group compounds and enabled the determination of pyrolitic/combustion PAHs dominancy.     

Chlorinated Hydrocarbons in Livers of American Mink (Mustela vison) and River Otter (Lutra canadensis) from the Columbia and Fraser River Basins, 1990–1992

We investigated chlorinated hydrocarbon contaminants in aquatic mustelid species on the Fraser and Columbia Rivers of northwestern North America. Carcasses of river otter (Lutra canadensis) (N=24) and mink (Mustela vison) (N=34) were obtained from commercial trappers during the winters of 1990–91 and 1991–92. Pooled liver samples were analyzed for organochlorine pesticides, polychlorinated biphenyls (PCBs), including non-ortho congeners, polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). Most samples contained detectable concentrations of DDE, PCBs, although there was substantial variability in patterns and trends among neighboring samples. Concentrations of DDE were in some mink and several otter samples from the lower Columbia River elevated (to 4700 g/kg wet weight); excluding one mink sample from the Wenatchee area, mean DDE levels generally decreased between 1978–79 and 1990–92. PCBs were present in all samples. PCB concentrations in otter livers collected from the lower Columbia were ten-fold lower than measured a decade previously; nevertheless, a sample taken near Portland had a mean concentration of 1500 g/kg, within a range of concentrations associated with reproductive effects in captive mink. Concentrations of 2,3,7,8-TCDD and TCDF were generally below detection limits, except for one otter collected near a pulp mill at Castlegar, on the upper Columbia, with 11 ng TCDD/kg in liver. Elevated concentrations of higher chlorinated PCDD/Fs, probably resulting from use of chlorophenolic wood preservatives, were found in both species; one otter sample from the lower Columbia had 2200 ng OCDD/kg. International TCDD toxic equivalent levels in mink (31 ng/kg) and otter (93 ng/kg) from the lower Columbia River approached toxicity thresholds for effects on reproduction in ranch mink.     

Assessment of enrichment factors and grain size influence on the metal distribution in riverbed sediments (Anll��ns River, NW Spain)

The metals distribution in the bed sediments of the Anllóns River was studied, with special emphasis on the evaluation of the metal distribution as a function of the granulometric fraction chosen for the analysis. Statistical significant differences between the distribution of K, Ca, Cr, Mn, As, Rb, Sr and Nb in the bulk (<2 mm) and fine fraction (<63 μm) were not found. Fe, Ni, Cu, Ga, Zr, Zn and Pb commonly appear in higher concentrations in the fine fraction, whereas Ti appears in higher concentrations in the bulk fraction. In general, it was observed that contamination phenomena tend to equalise the concentrations of both fractions, and this was mainly explained as the result of two processes. First, the formation of coatings over sands and, second, the formation of large aggregates (pseudo-sands) at sites located over basic rocks, whose chemical behaviour is closer to that of clays and could be responsible for significant adsorption processes. Normalisation techniques to evaluate contamination were applied by testing Nb, Sr, Rb or Ga as normaliser elements and by using crustal or shale average values for background concentrations. The most satisfactory result was obtained when using shale average values and Ga as the normaliser element. Arsenic was identified as the main contaminant of the basin, exceeding in all cases the low-effect reference values proposed by sediment quality guidelines and in two cases the medium-effect reference values. These sites were identified by multivariate techniques, which allow differentiating site 10 as affected by anthropogenic inputs related to past mining activities.     

Determination of heavy metal levels in water, sediment and tissues of tench (Tinca tinca L., 1758) from Beyşehir Lake (Turkey)

In the present study, some heavy metals (Cu, Fe, Zn and Mn) were seasonally determined in water, sediment and some tissues of fish Tinca tinca from Bey?ehir Lake, which is an important bird nesting and visiting area, a water source for irrigation and drinking. In the water, Fe has the highest concentrations among the studied metals. Generally, the metal concentrations increased in the hottest period decreased in warm seasons. Results for levels in water were compared with national and international water quality guidelines, as well as literature data reported for the lakes. Fe was the highest in sediment samples, also Cu and Zn were the highest in spring, while Fe and Mn were in autumn. Among the heavy metals studied, Cu and Mn were below the detection limits in some tissues. Generally, higher concentrations of the tested metals were found in the summer and winter, compared with those during the autumn and spring seasons. High levels of heavy metals were found in liver of T. tinca, while low levels in muscle samples. Metal concentrations in the muscle of examined fish were within the safety permissible levels for human consumption. The present study shows that precautions need to be taken in order to prevent further heavy metal pollution.     

Identification and quantification of microcystins from a Nostoc muscorum bloom occurring in Oukaïmeden River (High-Atlas mountains of Marrakech, Morocco)

Atmospheric BTEX [benzene, toluene, ethylbenzene, o-xylene and (m + p)-xylene] concentrations have been determined in the Naples metropolitan area (NMA) and in two suburban areas located on the north within about 25 km, during 2006. The pollutants were collected by passive samplers (24-h samplings), and analysed by GC-MS. In all the areas analysed the average atmospheric benzene concentrations were higher than the limit value fixed by the European Union for 2010 and in NMA the average concentration (9.8 microg m(-3)) also exceeded the limit fixed for 2006. High linear correlation coefficients between the average daily concentrations of the different BTEX are indicative of a single major source, most likely the vehicular traffic. The temporal and spatial distribution of BTEX relative concentrations suggest that massive emissions in NMA negatively affect the quality of the air in northern suburban areas, prevalently during the hottest months of the year, probably due to transport by local seasonal winds. The ratios between BTEX daily concentrations showed a clear dependence on the intensity of solar actinic flow, indicating a major role of photochemical processes in the air cleaning from these volatile organic pollutants.