This paper contributes to increase the knowledge of the contents and sources of heavy metals (Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn) to agricultural soils in Castellón province (Spain), a representative area of the European Mediterranean region. The surface horizons of 77 agricultural soils under vegetable crops were sampled and heavy metals were analysed by atomic absorption spectroscopy (AAS) after microwave extraction using the USEPA 3051A method. Mean heavy metal contents were similar to those obtained in other areas of this region. However, heavy metal contents (e.g. Cr, Pb) in some soils were above the maximum limit set in the 86/278/CEE Directive. Multivariate analysis (correlation analysis and principal component analysis - PCA) was performed so as to identify the sources of heavy metals to soils. Co, Fe and Ni were highly correlated amongst them (r > 0.800; p < 0.01), whereas Cr and Mn were less correlated with Co, Fe and Ni (r > 0.500; p < 0.01). Other relationships among heavy metals (i.e. Cu, Pb and Zn) were also identified, although correlation coefficients were not so high as those among Co, Fe and Ni (r < 0.500; p < 0.01). Contents of Co, Fe, Mn and Ni were interpreted to be mainly associated with parent rocks corresponding to the first principal component (PC1). On the other hand, Cd, Cu, Pb and Zn were interpreted to be mainly related to anthropogenic activities and comprised the second (Pb and Zn) and the third (Cd and Cu) principal components (PC2 and PC3, respectively), designated as anthropogenic components. Remarkably, Cr appears to be related in the study area to both the lithogenic and the anthropogenic components. Lithogenic elements were highly correlated with soil properties. Positive relationships with CEC (r > 0.200; p < 0.05) and clay (r > 0.400; p < 0.01), and negative relationships with carbonates (r > -0.400; p < 0.01) and sand (r > -0.300; p < 0.01) were observed. Anthropogenic elements were less correlated with soils properties, since these elements are generally more mobile because they form more soluble chemical species associated to anthropogenic sources. Particularly, no correlation was found between Cd and Zn and soil properties. These findings extend results achieved in other parts of the region, highlighting the need to set soil quality standards in order to declare soils affected by anthropogenic pollution, particularly in the case of anthropogenic metals such as Cd, Cu and Pb, and also Cr and Zn in some areas. Further knowledge from other areas in this region would improve the basis for proposing such standards at regional level, which is a priority objective in Europe according to the European Thematic Strategy for Soil Protection.

Agrichemical spills and discharges to soil can cause point-source contamination of surface and ground waters. When high contaminant concentrations inhibit natural attenuation in soils, chemical treatments can be used to promote degradation and allow application of treated soils to agricultural lands. This approach was used to remediate soil containing >650 mg atrazine, >170 mg metolachlor and >18,000 mg nitrate kg⁻¹. Results indicated a decrease in metolachlor concentration to <1 mg kg⁻¹ within 95 days of chemical treatment with zerovalent iron (Fe⁰, 5% w/w) and aluminum sulfate (Al₂(SO₄)₃, 2% w/w) but after one year >150 mg atrazine and >7000 mg nitrate kg⁻¹ remained. Laboratory experiments confirmed that subsequent additions of sucrose (table sugar) to the chemically pretreated soil promoted further reductions in atrazine and nitrate concentrations. Field-scale results showed that adding 5% (w/w) sucrose to windrowed and pretreated soil significantly reduced atrazine (<38 mg kg⁻¹) and nitrate (<2,100 mg kg⁻¹) concentrations and allowed for land application of the treated soil. These results provide evidence that zerovalent iron in combination with Al₂(SO₄)₃ and sucrose can be used for on-site, field-scale treatment of pesticide- and nitrate-contaminated soil.

Investigation of pollution sources and their impacts on ecosystems is important, not only for better understanding the responses of an ecosystem to pollutants, but also for making practicable prevention and control plans. In this study, ecological quality of three areas which received different source pollutants in Shanghai coast were evaluated and compared in four seasons using Shannon-Wiener index (H'), a benthic diversity index as an indicator of ecological quality of coastal waters. The genotoxicity and physical-chemical variables of water samples were also analyzed. The H' value indicated the ecological quality of Shanghai coastal waters was seriously impacted, and the ecological quality of two areas receiving waste discharges were significantly worse than that of the natural protection zone but not significantly different in four seasons. The positive genotoxic response was detected in most samples from two discharge zones but not detected in the samples from the natural protection zone. However, no significant difference was observed in water quality variables in the different coastal areas. Our study suggested that the point source pollution had significantly contributed to the genotoxicity of the coastal waters and impaired benthic assemblages, while the deterioration of ecological quality status was also critically impacted by the stressors from other sources.

Atrazine-contaminated soil may require remediation to mitigate ground and surface water contamination. We determined the effectiveness of nano zerovalent iron (nano ZVI) to dechlorinate atrazine (2-chloro-4ethylamino-6-iso-propylamino-1,3,5-triazine) in contaminated water and soil. This study determined the effects of iron sources, solution pH, Pd catalyst and presence of Fe or Al sulfate salts on the destruction of atrazine in water and soil. Our results indicate nano ZVI can be successfully used to remediate atrazine in water and soil. Aqueous solution of atrazine (30 mg l⁻¹) was treated with 2% (w/v) of nano ZVI and 5% (w/v) of commercial ZVI. Although, iron dose in nano ZVI treatment was less than that in commercial ZVI treatment, atrazine destruction kinetic rate (k obs) of nano ZVI treatment (1.39 days⁻¹) was around seven times higher than that of commercial ZVI treatment (0.18 days⁻¹). Reductive dechlorination was the major process in destruction of atrazine by nano ZVI. The dechlorination product was 2-ethyl-amino-4-isopropylamino-1,3,5-triazine. Lowering the pH from 9 to 4 increased the destruction kinetic rates of atrazine by nano ZVI. Moreover, nano ZVI/Pd enhanced destruction kinetic rates of atrazine (3.36 day⁻¹). Pd played the important role as a catalyst during treatment of atrazine by nano ZVI. Atrazine destruction kinetic rates were greatly enhanced in both contaminated water and soil treatments by nano ZVI when sulfate salts of Fe(II), Fe(III) or Al(III) was add with the following order of removal rates: Al (III) (2.23 day⁻¹) > Fe (III) (2.04 day⁻¹) > Fe(II) (1.79 day⁻¹). The same results were found in atrazine-nano ZVI-soil incubation experiments.

Biofilm development in wastewater treatment system by soil infiltration is often mentioned for its participation to purification efficiency and clogging zone formation. It appears necessary to understand its evolution in order to better control the operation of these systems. The objective of this study was to improve knowledge about the temporal evolution of the biofilm structure in the first centimetres of infiltration system. For this purpose, metabolic fingerprints by Biolog EcoPlate[trade mark sign] and molecular fingerprints by Ribosomal Intergenic Spacer Analysis (RISA) were carried out on sand, septic effluent and treated effluent samples from two experimental reactors supplied with different hydraulic loads collected at different times. The metabolic capabilities of sand microflora decreased in time. In the same way, molecular structure of the biofilm community changed and converged to similar structure in time. Principal components analysis on RISA gel revealed a “buffering effect” of the sand filter on the genetic structure of the bacterial community from treated effluent. The kinetics of evolution of the both metabolic and genetic fingerprints showed a reduction of the metabolic and genetic potentials of septic and treated effluents for the same times. The population dynamic within the biofilms appears interesting evidence in the comprehension of the operation of the treatment systems.

The theoretical basis of the proposed technique is the cumulative variation of ¹³⁷Cs measurements' squared-differences between a reference and other sites. The change of the cumulative squared-differences with distance from the reference site is referred to as the point cumulative semivariogram (PCSV), which provides appropriate measure of cumulative similarity. Inspection of individual experimental PCSV provides local interpretation about the ¹³⁷Cs radioactivity concentration around each site, whereas collective inspections provide possibility for grouping similar sites and hence identifying homogeneous sub-areas within the study area. It is also possible to prepare ¹³⁷Cs radioactivity concentration maps based on pre-specified distances in each experimental PCSV, which lead to similarity levels. Such maps provide appreciation of ¹³⁷Cs radioactivity concentration regional dependence in Keban Dam Lake, Turkey. Apart from the individual PCSV interpretations, the whole lake is divided into four distinctive classes.

Urine-treated soils make a significant contribution to gaseous N losses to the atmosphere. Our goal was to investigate the influence of clay type and content on ammonia (NH₃) and nitrous oxide (N₂O) emissions from urine under different wetting-drying soil conditions and to relate these results to urine-N transformation processes in soil. Three types of silt loam soils and synthetic sand-clay aggregates with three different clay-dominated materials (kaolinite, montmorillonite and vermiculite) were used in this laboratory study. Bulk soil, 4-4.75 mm and 9.5-11.2 mm aggregates were incubated with synthetic urine at 50% and 75% saturation under aerobic conditions. Repeated urine application affected the properties of the aggregates depending on the type of clay present. Greater clay content increased aggregate stability and reduced NH₃ volatilization. The variation in clay ammonium (NH₄ ⁺) fixation capacities was reflected in NH₃ volatilization as well as in the onset of N₂O emissions, occurring first from kaolinite-dominated and last from vermiculite-dominated soils. Nitrous oxide production was greater in aggregates than in bulk soil, a difference that consistently increased with repeated urine applications for kaolinitic and vermiculitic treatments. A dual-peak N₂O emission pattern was found, with the second maximum increasing with the number of urine applications. Emission of ¹⁵N-labeled N₂ was found at 75% saturation in kaolinite and vermiculite-dominated samples. Anaerobic conditions were less pronounced with montmorillonite-dominated samples because shrink-swell action caused aggregate breakage.

An intensive survey of mercury speciation was performed at a site on the Upper St. Lawrence River near Cornwall, Ontario, Canada with a history mercury contamination in sediments. Surface sediments were collected every 1.50 h. Total mercury (Hgtotal), methylmercury (MeHg), organic carbon, inorganic and organic sulphur were determined in the solid fraction. Dissolved Hgtotal, MeHg and dissolved organic carbon (DOC) were measured in pore waters. Concentrations of Hgtotal in the upper layers (first 5 cm) were high, ranging from 1.42 to 25.8 nmol g-¹ in solids and from 125 to 449 pM in pore waters. MeHg levels were also high, ranging from 4.34 to 34.1 pmol g-¹ in solids and from 40 to 96 pM in pore waters. This amounts to up to 1.4% of Hgtotal present as MeHg in solids and 64% in pore waters. A daily pattern for Hgtotal was observed in the solid fraction. The MeHg distribution in solids and pore waters was not correlated with Hgtotal or DOC, suggesting that the concentrations of MeHg are probably more influenced by the relative rates of methylation/demethylation reactions in the sediment-water interface. Acid volatile sulphide levels and DOC were inversely correlated with organic sulphur (Sorg) levels suggesting that both parameters are involved in the rapid production of Sorg. A positive correlation was also observed between Hgtotal and Sorg in solids (R = 0.87, p < 0.01) illustrating the importance of organic sulphur in the retention and distribution of Hg in the solid fraction of the sediments. The results suggest that variations of Hgtotal concentrations in Upper St. Lawrence River surface sediments were strongly influenced by the formation/deposition/retention of organic sulphur compounds in the sediment-water interface.

Mercury and organic carbon concentrations vary dynamically in streamwater at the Sleepers River Research Watershed in Vermont, USA. Total mercury (THg) concentrations ranged from 0.53 to 93.8 ng/L during a 3-year period of study. The highest mercury (Hg) concentrations occurred slightly before peak flows and were associated with the highest organic carbon (OC) concentrations. Dissolved Hg (DHg) was the dominant form in the upland catchments; particulate Hg (PHg) dominated in the lowland catchments. The concentration of hydrophobic acid (HPOA), the major component of dissolved organic carbon (DOC), explained 41-98% of the variability of DHg concentration while DOC flux explained 68-85% of the variability in DHg flux, indicating both quality and quantity of the DOC substantially influenced the transport and fate of DHg. Particulate organic carbon (POC) concentrations explained 50% of the PHg variability, indicating that POC is an important transport mechanism for PHg. Despite available sources of DHg and wetlands in the upland catchments, dissolved methylmercury (DmeHg) concentrations in streamwaters were below detection limit (0.04 ng/L). PHg and particulate methylmercury (PmeHg) had a strong positive correlation (r ² = 0.84, p < 0.0001), suggesting a common source; likely in-stream or near-stream POC eroded or re-suspended during spring snowmelt and summer storms. Ratios of PmeHg to THg were low and fairly constant despite an apparent higher methylmercury (meHg) production potential in the summer. Methylmercury production in soils and stream sediments was below detection during snowmelt in April and highest in stream sediments (compared to forest and wetland soils) sampled in July. Using the watershed approach, the correlation of the percent of wetland cover to TmeHg concentrations in streamwater indicates that poorly drained wetland soils are a source of meHg and the relatively high concentrations found in stream surface sediments in July indicate these zones are a meHg sink.

Communities of aquatic macroinvertebrates, fish density and biomass, and environmental variables were investigated in three Patagonian mountain rivers affected by urbanization. The rivers Las Minas, Esquel and Carbón that flow through the towns of Cholila, Esquel and Corcovado, respectively (northwest Chubut, Argentina) were selected to assess the degree of impairment. A reference site and an urban site were established on each river. Water quality variables including conductivity, major nutrients, total suspended solids (TSS) and dissolved oxygen, habitat conditions and quality of riparian ecosystems were investigated in autumn, winter, spring and summer 2005–2006. Macroinvertebrates were sampled concurrently in three riffles and three pools at each site. Invertebrate species richness, EPT richness, the Shannon–Weaver diversity index, % EPT density, and the BMPS index were lower at urban sites, whereas % collectors increased. The most impaired site was below Esquel, the largest town. Senzilloides panguipulli (Plecoptera), Polypedilum and Rheotanytarsus species (Diptera: Chironomidae), Nais communis (Oligochaeta) and Meridialaris chiloeensis (Ephemeroptera) dominated assemblages at reference and moderately impaired sites in summer, whereas the strongly polluted reach below Esquel had low flow in summer and a community dominated by Limnodrilus spp. (Oligochaeta), Helobdella spp. (Hirudinea), and two Hyallela species (Amphipoda). Canonical correspondence analysis indicated that ammonia, conductivity and TSS were important variables structuring invertebrate assemblages. In contrast, fish density and biomass varied in a non-systematic manner among sites. Overall, urbanization resulted in varying degrees of habitat degradation, sedimentation and nutrient enrichment that were reflected by the macroinvertebrate assemblages, which can be used effectively to monitor the effects of urban communities on Patagonian mountain streams.