Multi-residues analysis of pre-emergence herbicides in fluvial sediments: application to the mid-Garonne River

Contamination of man and ecosystems by pesticides has become a major environmental concern. Whereas many studies exist on contamination from agriculture, the effects of urban sources are usually omitted. Fluvial sediment is a complex matrix of pollutants but little is known of its recent herbicide content. This study proposes a method for a fast and reliable analysis of herbicides by employing the accelerated solvent extractor (ASE). The aim of the study is to show the impact of a major town (Toulouse) on the herbicide content in the river. In this study, three herbicide families (i.e.s-triazine, substituted ureas and anilides) were analysed in fluvial sediment fractions at 11 sampling sites along the mid-Garonne River and its tributaries. River water contamination by herbicides is minor, except for at three sites located in urban areas. Among the herbicidal families studied, urban and suburban areas are distinguished from rural areas and were found to be the most contaminated sites during the study period, a winter low-water event. The herbicide content of the coarse sediment fractions is about one third of that found in the fine fractions and usually ignored. The distribution of pesticide concentrations across the whole range of particle sizes was investigated to clarify the role of plant remains on the significant accumulation in the coarse fractions.     

The relationship of mineral and geochemical composition to artificial radionuclide partitioning in Yenisei river sediments downstream from Krasnoyarsk

Discharges from the Mining-and-Chemical Combine (MCC) of Rosatom, downstream from Krasnoyarsk, resulted in radioactive contamination of sediments of the River Yenisei. The concentration of artificial gamma-emitting radionuclides (¹³⁷Cs, ⁶⁰Co, ¹⁵²Eu, and ²⁴¹Am) was determined with the objective to analyze the migration processes leading to the transport of these radionuclides. The content of artificial radionuclides in the surface layers of the study area varied in wide ranges: ¹³⁷Cs—318–1,800 Bq/kg, ⁶⁰Co—87–720 Bq/kg, ¹⁵²Eu—12–287 Bq/kg and ²⁴¹Am—6–76 Bq/kg. There was a sequence of migration of radionuclides investigated in the surface layer of sediments that were collected in the near zone of influence of the MCC: ²⁴¹Am ≈ ¹⁵²Eu > ⁶⁰Co > ¹³⁷Cs. Radionuclide species have been found to be directly related to sediment structure and composition.     

Effects of an oil spill on soil physico-chemical properties of a spill site in the Niger Delta Area of Nigeria

Physico-chemical analysis of soil samples at an oil spill site in the Niger Delta Area of Nigeria showed that the total hydrocarbon content of top soil layers ranged from 0.8 to 12.4 ppm in the heavy impact zone and the oil had penetrated to a depth of 7.2 m. Hydrocarbon concentration in the medium impact zone ranged from 0.02 to 0.40 ppm while hydrocarbons were not detected in 75% of samples from the unimpacted reference zone. Measurement of heavy metal concentrations in the soils revealed a significant build-up (p<0.05) of lead, iron and zinc in the heavy impact zone. Other parameters including electrical conductivity, exchangeable cations, available phosphorus and total nitrogen in impacted soils were comparatively low while the total organic carbon was high, compared with the reference site. Textural class of soil from the different depths showed a predominantly brown sand at the top soil, loamy sand at medium depths and grey coarse sand at greater depths.     

Factors controlling the accumulation of metals within fluvial systems

The magnitude and distribution of European Community (EC) regulated List I and List II metals and metalloids have been investigated in two lowland river systems in East Anglia, U.K. A combination of sediment and water quality data identified municipal sewage treatment work discharges as the main metal input sources to the river systems and identified two main areas of metal contamination: the Pix Brook, downstream of Letchworth STW on the River Ivel, and a 14 km enrichment zone adjacent to Whitlingham STW on the River Yare. The basement geology, flow dynamics, distance from point sources and sediment type were identified as important controls upon the magnitude and spatial distribution of metal contaminants.     

Trace metals in the bottom sediments of the harbour of Lagos,Nigeria

A study has been made of the heavy metal contents of sediments in the harbour of Lagos which receives a variety of human and industrial wastes. The results indicate three areas with low, medium and high pollution by heavy metals. The harbour in which most shipping activities are concentrated has a low level of pollution. Both other areas with medium and high pollution by heavy metals are located at the entrance and in northwest sections of the harbour respectively, which receive effluents from industries and communities.     

Comparison of two metal surveys by moss Tortula ruralis in Budapest, Hungary

Moss transplants of Tortula ruralis were used as active biomonitoring organisms as part of a monitoring study to assess the metals (Al, Cd, Cu, Cr, Fe, Ni, Pb, V and Zn) associated with ambient particles on mosses in Budapest, the capital town of Hungary. The moss samples were collected in a nature conservation area from a semi-arid sand grassland (Festucetum vaginatae danubiale), less than 1 month before transplantation. Moss cushions were exposed to pollution in Budapest during October–November 1993 and February–March 1994. In the study area, 16 sites were marked out as measuring sites, in accordance with the structure of the city. A similar stand was established in the Botanical Gardens of the Szent István University in Gödöll? as a control site. ICP-AES analysis of moss for metals showed the ability of Tortula ruralis to accumulate the metals under study. Control site showed lower impact in comparison to the other sites.     

Mercury in the sediments of Vembanad Lake,western coast of India

Mercury, a global pollutant, is popping up in places where it was never expected before and it burdens in sediments and other non-biological materials. It is estimated to have increased up to five times the pre-human level due to anthropogenic activities. Vembanad backwaters, one of the largest Ramsar site in India, which have extraordinary importance for its hydrological function, are now considered as one of the mercury hot spots in India. In this study, surface sediment samples of Vembanad Lake and nearshore areas have been seasonally analysed for total mercury and methyl mercury concentrations while the core sediment samples were analysed for total mercury. The results showed that the northern part of the lake was more contaminated with mercury than the southern part. The mercury concentration was relatively high in the subsurface sediment samples, indicating the possibility of historic industrial mercury deposition. A decreasing trend in the mercury level towards the surface in the core sediment was also observed. The geochemical parameters were also analysed to understand the sediment mercury chemistry. Anoxic conditions, pH and organic carbon, sulphur and Fe determined the presence of various species of mercury in the sediments of Vembanad Lake. The prevailing physical and geochemical conditions in Vembanad Lake have indicated the chances of chemical transformation of mercury and the potential hazard if the deposited mercury fractions are remobilised.     

Metal speciation studies in the aquifer sediments of Semria Ojhapatti,Bhojpur District,Bihar

The pollution of aquifer sediments by heavy metals has assumed serious concern due to their toxicity and accumulative behavior. Changes in environmental conditions can strongly influence the behavior of both essential and toxic elements by altering the forms in which they occur and therefore quantification of the different forms of metal is more meaningful than total metal concentrations. In this study, fractionation of metal ions in aquifer sediments of Semria Ojhapatti area, Bhojpur district, Bihar has been studied to determine the ecotoxic potential of metal ions. The investigations suggest that iron, copper, and arsenic have a tendency to remain associated in the following order residual > reducible > acid-soluble > oxidizable; manganese and zinc have tendency to be associated as residual > acid-soluble > reducible > oxidizable. The risk assessment code reveals that manganese and zinc occur in significant concentration in acid-soluble fraction and therefore comes under the high risk category and can easily enter the food chain. Most of the iron, copper, and arsenic occur as immobile fraction (i.e. residual) followed by its presence in reducible fraction and would pose threat to the water quality due to changing redox conditions. The metal enrichment factor in the study area shows moderate to significant metal enrichment in the aquifer sediments which may pose a real threat in near future. The geo-accumulation index of metals also shows that the metals lie in the range of strongly contaminated (for iron at shallow depths) to moderately contaminated to uncontaminated values.     

Distribution and accumulation of heavy metals in the sediments of Akkaya Dam,Nigde, Turkey

Twenty-one surface sediment samples were collected from Akkaya Dam. Heavy metal concentrations (Mo, Cu, Pb, Zn, Ni, Co, Mn, Fe, Cr, As, V and Cd), grain size, organic carbon and carbonate contents were studied in order to assess the extent of environmental pollution and to discuss the origin of these contaminants in sediments of dam. The sediments in the study area are mostly very fine sands. However, mud was observed in the northeast of the dam. Sediment pollution assessment was carried out using enrichment factor. The calculation of enrichment factors showed that Mo is depleted by 1.0 whereas Cu, Pb, Zn, Ni, Co, Mn, As, V, Cr and Cd are enriched by 3, 5.4, 7, 2.7, 2.2, 3.4, 42.3, 2.1, 1.8 and 7.2, respectively. Relatively high concentrations heavy metals occurred in north (textile industry area) and east (Karasu River) due to enrichment controlled by anthropogenic wastes. The results of correlation analysis show low–medium positive and negative correlations among metals, grain size, carbonate contents and organic carbon and indicate that heavy metals in sediments of the Akkaya Dam have different anthropogenic sources.     

Determination and speciation of heavy metals in sediments of the Juru River,Penang, Malaysia

The Juru River flows through largely urbanized areas and is grossly polluted by domestic wastes and discharges from pig farms. Other than carrying highly polluting organic materials, these wastes are also contaminated with heavy metals. To ascertain the extent of heavy metal pollution in the river, total and non-residual concentrations of Cu, Pb, Zn, Mn and Fe in sediment samples collected along the river were determined. The results indicate that both the total and non-residual metal concentrations in sediments can successfully be used to identify heavy metal pollution sources. The speciation of Zn, Mn and Fe in the sediment samples were investigated using a sequential leaching technique which identifies the elements among six operationally defined host fractions: (1) exchangeable, (2) carbonate and surface-associated, (3) easily reducible, (4) moderately reducible, (5) bound to organic matter and sulphides and (6) residual. The results indicate that Zn is mainly associated with the reducible fractions. Zn and Fe found in the moderately reducible fraction are significantly correlated, indicating that iron oxides is the preferred host phase by Zn.     

Heavy metal concentrations in the surface marine sediments of Sfax Coast, Tunisia

Sixty-seven surface marine sediment samples in the <63 ?? m fraction collected from the coast of Sfax (Tunisia) were analyzed by inductively coupled plasma-atomic emission spectrometry for seven heavy metals (Pb, Ni, Cu, Cr, Zn, Cd, and Fe). Metal concentrations were compared with natural values, marine sediment quality standards, and also with other results concerning sediments from several Mediterranean coasts. The study of their spatial distributions refined by complementary approaches including principal component analysis, enrichment factors, and geoaccumulation index showed a significant impact of multiple anthropogenic sources. These included industrial sources and municipal discharges of the urban Sfax and also non-controlled discharges in rural zones close to the coastline. Moderate pollution of sediments, especially by Pb, Zn, and Ni, was shown to exist in localized sites. Besides, it was shown that other sites, slightly to highly enriched in terms of Cu, Cr, and Cd, are characterized by a quality of sediments varying from unpolluted to moderately polluted.     

Lead in hawks,falcons and owls downstream from a mining site on the Coeur d'Alene River,Idaho

Mining and smelting at Kellogg-Smelterville, Idaho, resulted in high concentrations of lead in Coeur d'Alene (CDA) River sediments and the floodplain downstream, where American Kestrels (Falco sparverius), Northern Harriers (Circus cyaneus), Red-tailed Hawks (Buteo jamaicensis), Great Horned Owls (Bubo virginianus), and Western Screech-owls (Otus kennicotti) nested. Nestling American Kestrels contained significantly higher (P=0.0012) blood lead concentrations along the CDA River (0.24 µg/g, wet wt) than the nearby reference area (0.087 µg/g). A 35% inhibition of blood -aminolevulinic acid dehydratase (ALAD) in nestling Northern Harriers (P=0.0001), 55% in nestling American Kestrels (P=0.0001) and 81% in adult American Kestrels (P=0.0004) provided additional evidence of lead exposure in the CDA River population. In nestling American Kestrels and Northern Harriers, ALAD activity was negatively correlated with lead in blood. An earlier report on Ospreys (Pandion haliaetus) showed slightly less inhibition of ALAD than in American Kestrels, but no significant reduction in hemoglobin or hematocrit and no negative influence on production rates. The adult and nestling American Kestrels along the CDA River contained about twice as much blood lead as Ospreys during the same years (adult 0.46 vs. 0.20 µg/g, and nestling 0.24 vs. 0.09 µg/g), but adults showed a 7.5% reduction in hemoglobin (P=0.0356) and nestlings an 8.2% reduction in hemoglobin (P=0.0353) and a 5.8% reduction in hematocrit (P=0.0482). We did not observe raptor deaths related to lead, and although the production rate for American Kestrels was slightly lower along the CDA River, we found no significant negative relation between productivity and lead. Limited data on the other raptors provide evidence of exposure to lead along the CDA River. Several traits of raptors apparently reduce their potential for accumulating critical levels of lead which is primarily stored in bones of prey species.The U.S. Government right to retain a non-exclusive, royalty free licence in and to any copyright is acknowledged.     

Geochemical evaluation of present-day Tuul River sediments, Ulaanbaatar basin, Mongolia

The Tuul River flows through the Ulaanbaatar basin of Mongolia and is the main source of water for the capital city, Ulaanbaatar. The Tuul catchment can be divided into three parts around Ulaanbaatar (upper, middle, and lower), according to the extent of urbanization. Sixteen surface water and groundwater samples were collected to evaluate present-day water quality and 34 stream sediment samples taken to examine their geochemical composition in relation to provenance and to assess the impact of urban activity on heavy metal accumulation. Groundwater quality in the upper and central water sources was adequate, but high concentrations of NO ₃ ^? were found in the lower water source. Heavy metal concentrations in the sediments are evaluated by comparison with average upper continental crust (UCC) values, coupled with ecological risk assessment by reference to sediment quality guidelines (SQG). The results show average abundances of potentially toxic metals such as As, Pb, Zn, Cu, Ni, Cr, and V are higher in the middle part (within the city) than in the upper and lower parts. However, all three parts show depletion in some chalcophile and high field strength elements (Cu, Ni, Cr, Sr, Nb, Zr, Th, Sc) relative to UCC, indicating that the river sediments were derived from a highly felsic crustal source. The assessment using SQG shows As and Cr are present in levels that cause adverse aquatic biological effects. Although concentrations of Pb, Zn, Cu, and Ni are generally below their respective threshold effect levels, in the middle reaches, values increase and border on the probable effect level. This suggests significant anthropogenic contamination in the urban areas, increasing values above a naturally low regional background.     

Assessment of some heavy metals in surface sediments of the Aqaba Gulf, Egypt

Aqaba Gulf is an economically important marine environment in Egypt. Its coastal area was subjected to anthropogenic impact of urbanization and economic development during the last decades. The study was oriented to investigate the distribution as well as assess the heavy metal pollution status (Fe, Mn, Zn, Ni, Co, Cr, Cu, and Cd) in its surface sediment. Large heavy metals fluctuations were detected along the studied area. The results pointed out to the highly significant correlations among Fe, Cu, Ni, and Co heavy metals and their similar lithogenic origin beside their input sources. The sediment quality was performed by using the geo-accumulation index (I (geo)) and different sediment criteria guidelines; China State Bureau of Quality and Technical Supervision (CSBTS), and Canadian guidelines. Among the studied heavy metals, Cd was the only metal that showed moderate pollution for I (geo) as well as it exceeded the primary and the secondary criteria of CSBTS and the threshold effect level of the Canadian guidelines (TEL). On the other hand, the other heavy metals were within the natural background levels.     

Forensic fingerprinting and source identification of the 2009 Sarnia (Ontario) oil spill

This paper presents a case study in which integrated forensic oil fingerprinting and data interpretation techniques were used to characterize the chemical compositions and determine the source of the 2009 Sarnia (Ontario) oil spill incident. The diagnostic fingerprinting techniques include determination of hydrocarbon groups and semi-quantitative product-type screening via gas chromatography (GC), analysis of oil-characteristic biomarkers and the extended suite of parent and alkylated PAH (polycyclic aromatic hydrocarbon) homologous series via gas chromatography-mass spectrometry (GC-MS), determination and comparison of a variety of diagnostic ratios of "source-specific marker" compounds, and determination of the weathering degree of the spilled oil, and whether the spilled oil hydrocarbons have been mixed with any other "background" chemicals (biogenic and/or pyrogenic hydrocarbons). The detailed chemical fingerprinting data and results reveal the following: (1) all four samples are mixtures of diesel and lubricating oil with varying percentages of diesel to lube oil. Both samples 1460 and 1462 are majority diesel-range oil mixed with a smaller portion of lube oil. Sample 1461 contains slightly less diesel-range oil. Sample 1463 is majority lubricating-range oil. (2) The diesel in the four diesel/lube oil mixture samples was most likely the same diesel and from the same source. (3) The spill sample 1460 and the suspected-source sample 1462 have nearly identical concentrations and distribution patterns of target analytes including TPHs, n-alkane, PAHs and biomarker compounds; and have nearly identical diagnostic ratios of target compounds as well. Furthermore, a perfect "positive match" correlation line (with all normalized ratio data points falling into the straight correlation line) is clearly demonstrated. It is concluded that the spill oil water sample 1460 (#1, from the water around the vessel enclosed by a boom) matches with the suspected source sample 1462 (#3, from the vessel engine room bilge pump). (4) From the n-alkane and PAH analysis, it appears that the oil in the spill sample 1460 is slightly more weathered in comparison with sample 1462. The minor differences in fingerprints of two samples were most likely caused by weathering effects. (5) Sample 1461 (#2, from the vessel engine room bilge) and sample 1463 (#4, from the vessel bilge waste collection tank) demonstrated significantly different fingerprints and diagnostic ratios of target compounds from that of spill sample 1460. This was caused most likely by percentages of diesel to lube oil in these two samples different from that in spill sample 1460.     

Heavy metal pollution in water and sediments in the Kabini River, Karnataka, India

Critical to habitat management is the understanding of not only the location of animal food resources, but also the timing of their availability. Grizzly bear (Ursus arctos) diets, for example, shift seasonally as different vegetation species enter key phenological phases. In this paper, we describe the use of a network of seven ground-based digital camera systems to monitor understorey and overstorey vegetation within species-specific regions of interest. Established across an elevation gradient in western Alberta, Canada, the cameras collected true-colour (RGB) images daily from 13 April 2009 to 27 October 2009. Fourth-order polynomials were fit to an RGB-derived index, which was then compared to field-based observations of phenological phases. Using linear regression to statistically relate the camera and field data, results indicated that 61% (r (2)?= 0.61, df = 1, F?= 14.3, p?= 0.0043) of the variance observed in the field phenological phase data is captured by the cameras for the start of the growing season and 72% (r (2)?= 0.72, df = 1, F?= 23.09, p?= 0.0009) of the variance in length of growing season. Based on the linear regression models, the mean absolute differences in residuals between predicted and observed start of growing season and length of growing season were 4 and 6?days, respectively. This work extends upon previous research by demonstrating that specific understorey and overstorey species can be targeted for phenological monitoring in a forested environment, using readily available digital camera technology and RGB-based vegetation indices.     

Levels, distribution, and risk assessment of organochlorines in surficial sediments of the Red Sea coast, Egypt

The analyses of environmentally persistent pollutants like polychlorinated biphenyls (PCBs), hexachlorocyclohexane (HCH) isomers, and dichlorodiphenyltrichloroethane (DDT) and its metabolites in surficial sediment samples collected from 17 locations along with the coast of the Red Sea in Egypt were carried out using gas chromatography–mass spectrometry. Several potential organic contaminants from agricultural (e.g., DDT and its breakdown products, lindane, endrin, dieldrin, and endosulfan) and industrial (PCBs) sources were measured. The levels of 20 organochlorine pesticides (OCPs) and ten PCB congeners in sediment collected from 17 stations along ~1,200 km were investigated. Concentrations of PCBs, HCHs, DDTs, and cyclodienes ranged from 0.40 to 6.17, 0.01 to 0.09, n.d. to 0.46, and 0.08 to 0.90 ppb dry weight. Two statistical programs were applied on the data (principal component analysis, PCA, and cluster analysis, CA), and it was concluded that it is impossible to predict the distribution patterns of the OCPs in a contaminated area. Risk assessment of the organochlorines contaminated in the sediments of the studied area was investigated.