Effects of middle-term land reclamation on nickel soil-water interaction: a case study from reclaimed salt marshes of Po River Delta,Italy

Reclaimed salt marshes are fragile environments where water salinization and accumulation of heavy metals can easily occur. This type of environment constitutes a large part of the Po River Delta (Italy), where intensive agricultural activities take place. Given the higher Ni background of Po River Delta soils and its water-soluble nature, the main aim of this contribution is to understand if reclamation can influence the Ni behavior over time. In this study, we investigated the geochemical features of 40 soils sampled in two different localities from the Po River Delta with different reclamation ages. Samples of salt marsh soils reclaimed in 1964 were taken from Valle del Mezzano while soils reclaimed in 1872 were taken nearby Codigoro town. Batch solubility tests and consecutive determination of Ni in pore-water were compared to bulk physicochemical compositions of soils. Bulk Ni content of the studied soils is naturally high, since these soils originated from Po River sediments derived from the erosion of ultramafic rocks. Moreover, it seems that Ni concentration increases during soil evolution, being probably related to the degradation of serpentine. Instead, the water-soluble Ni measured in the leaching tests is greater in soils recently reclaimed compared to the oldest soils. Soil properties of two soil profiles from a reclaimed wetland area were examined to determine soil evolution over one century. Following reclamation, pedogenic processes of the superficial horizons resulted in organic matter mineralization, pH buffer, and a decrease of Ni water solubility from recently to evolved reclaimed soil.     

Lichen biomonitoring of trace metals in the Pistoia area (central northern Italy)

The epiphytic lichen Parmelia caperata (L.) Ach. was used as bioaccumulator of the heavy metals Cd, Cr, Cu, Hg, Ni, Pb and Zn in the environs of the town of Pistoia (central northern Italy). The concentrations of Cd, Cr, Ni, Hg and Pb were comparable with those found in areas not subject to atmospheric pollution. Copper and especially Zn were found in rather high concentrations. Fertilizers and pesticides were the main source of atmospheric contamination.     

Organic and inorganic diffuse contamination in urban soils: the case of Torino (Italy)

Soils in urban parks are useful tracers of diffuse contamination and could represent a potential health risk for citizens. Soils in the parks of Torino, Italy, were sampled and analysed for a broad range of organic and inorganic contaminants. Concentrations of potentially toxic elements, PAHs, PCBs and polychlorinated dibenzo-p-dioxins and dibenzofurans were often above national legislation limits, and higher than surrounding rural areas or than other cities. Mean concentrations were 233 mg kg(-1) for Cr, 164 mg kg(-1) for Ni, 124 mg kg(-1) for Pb and 170 mg kg(-1) for Zn. Other inorganic contaminants such as Cd, As, and Hg showed high concentrations in some soils. Organic contaminants were also found to be enriched in the sampled parks (e.g. maximum concentrations of PCDDs/DFs and PCBs were 12.6 ng kg(-1) and 0.310 mg kg(-1), respectively). Data from this study reveal an important enrichment of parks for some contaminants, reflecting the intensity of phenomena of diffuse contamination. Historical parks presented the highest degree of contamination, suggesting that the age of soils rather than their proximity to sources of emissions is a key factor in determining soil contamination. Data obtained in this study could be of help in the investigation and remediation practices of urban contaminated sites within large cities.     

Accumulation of heavy metals in leaf vegetables from agricultural soils and associated potential health risks in the Pearl River Delta,South China

This study investigated the extent of heavy metal accumulation in leaf vegetables and associated potential health risks in agricultural areas of the Pearl River Delta (PRD), South China. Total concentrations of mercury (Hg), cadmium (Cd), lead (Pb), chromium (Cr) and arsenic (As) were determined in 92 pairs of soil and leaf vegetable (flowering Chinese cabbage, lettuce, pakchoi, Chinese cabbage, loose-leaf lettuce, and Chinese leaf mustard) samples collected from seven agricultural areas (cities). The bioconcentration factors (BCF) of heavy metals from soil to vegetables were estimated, and the potential health risks of heavy metal exposure to the PRD residents through consumption of local leaf vegetables were assessed. Results showed that among the six leaf vegetables, pakchoi had the lowest capacity for heavy metal enrichment, whereas among the five heavy metals, Cd had the highest capacity for transferring from soil into vegetables, with BCF values 30-fold those of Hg and 50-fold those of Cr, Pb and As. Sewage irrigation and fertilization were likely the main sources of heavy metals accumulated in leaf vegetables grown in agricultural areas of the PRD region. Different from previous findings, soil pH had no clear effect on metal accumulation in leaf vegetables. Despite a certain degree of metal enrichment from soil to leaf vegetables, the PRD residents were not exposed to significant health risks associated with consumption of local leaf vegetables. Nevertheless, more attention should be paid to children due to their sensitivity to metal pollutants.     

Spatial scales of variation in lichens: implications for sampling design in biomonitoring surveys

The variability of biological data is a main constraint affecting the quality and reliability of lichen biomonitoring surveys for estimation of the effects of atmospheric pollution. Although most epiphytic lichen bioindication surveys focus on between-site differences at the landscape level, associated with the large scale effects of atmospheric pollution, current protocols are based on multilevel sampling, thus adding further sources of variation and affecting the error budget. We test the hypothesis that assemblages of lichen communities vary at each spatial scale examined, in order to determine what scales should be included in future monitoring studies. We compared four sites in Italy, along gradients of atmospheric pollution and climate, to test the partitioning of the variance components of lichen diversity across spatial scales (from trunks to landscapes). Despite environmental heterogeneity, we observed comparable spatial variance. However, residuals often overcame between-plot variability, leading to biased estimation of atmospheric pollution effects.     

Pesticide residues in soils, sediments, and vegetables in the Red River Delta, northern Vietnam

This study assessed pesticide residues in soils, sediments, and vegetables in the Xuan Khe and Hop Ly communes located along the Chau Giang River in the Red River Delta, northern Vietnam. Samples were collected from agricultural areas within and outside of embankments built to prevent flooding. In Xuan Khe, the soils outside of the embankment were more clayey with higher organic matter contents compared with the inside, due to selective deposition during river flooding. Many of the soils contained significant amounts of pesticides including dichlorodiphenyltrichloroethane (DDT), dicofol, isoprothiolane, and metalaxyl although their levels were below the maximum allowable concentration set by the Vietnamese government. The spectrum of DDT derivatives found suggested that the source of DDTs was not contaminated dicofol. Soils in Hop Ly resembled soils in Xuan Khe but were relatively sandy; one field showed appreciable contents of DDT derivatives. The ratios of (p,p ^′-dichlorodiphenyldichloroethylene + p,p ^′-dichlorodiphenyldichloroethane)/∑DDT in the surface and subsurface soils in Hop Ly were 0.34 and 0.57, suggesting that the DDTs originated from recent application. Pesticide residues in soils were not likely to translocate into vegetable crops, except for metalaxyl. High concentrations of cypermethrins in kohlrabi leaves could be ascribed to foliar deposition.     

Concentrations and inventories of polycyclic aromatic hydrocarbons and organochlorine pesticides in watershed soils in the Pearl River Delta,China

The concentration levels, source, and inventories of polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides (OCPs) in 55 surface vegetable soils in the watershed of the Pearl River Delta (PRD) were analyzed and compared with those of the surface sediments in the Pearl River Estuary (PRE) and northern South China Sea (SCS). The 16 priority PAHs on US EPA list range from 58 to 3,077 microg/kg (average: 315 microg/kg). The concentrations of DDTs and HCHs range from 3.58 to 831 microg/kg (average: 82.1 microg/kg) and from 0.19 to 42.3 microg/kg (average: 4.42 microg/kg). The ratios of DDT/ (DDD+DDE) are higher than 2 in majority of the soil samples, suggesting that DDT contamination still exists. The PAH ratios suggest that the source of PAHs is petroleum, and combustion of fossil fuel, biomass, and coal. The average concentrations of PAHs and the linear regression slope between PAHs and TOC for the soils and the sediments are quite similar. It was estimated that the soil mass inventories at 0-20 cm depth are 1,292 metric tons for PAHs and 356 metric tons for OCPs in the studied region. The average PAHs inventory per unit area for the soil samples investigated in PRD is about 0.86 time that of surface sediments in the Pearl River Estuary, and about 2.43 times that of surface sediments in the northern South China Sea. PAHs in the soils in PRD have similar source to those of the surface sediments in PRE. All of those may suggest that PAHs in PRE and SCS are probably mainly inputted from the soils in PRD via soil erosion and river transport.     

A methodology for treating missing data applied to daily rainfall data in the Candelaro River Basin (Italy)

Environmental time series are often affected by the “presence” of missing data, but when dealing statistically with data, the need to fill in the gaps estimating the missing values must be considered. At present, a large number of statistical techniques are available to achieve this objective; they range from very simple methods, such as using the sample mean, to very sophisticated ones, such as multiple imputation. A brand new methodology for missing data estimation is proposed, which tries to merge the obvious advantages of the simplest techniques (e.g. their vocation to be easily implemented) with the strength of the newest techniques. The proposed method consists in the application of two consecutive stages: once it has been ascertained that a specific monitoring station is affected by missing data, the “most similar” monitoring stations are identified among neighbouring stations on the basis of a suitable similarity coefficient; in the second stage, a regressive method is applied in order to estimate the missing data. In this paper, four different regressive methods are applied and compared, in order to determine which is the most reliable for filling in the gaps, using rainfall data series measured in the Candelaro River Basin located in South Italy.     

Passive air sampling of DDT, chlordane and HCB in the Pearl River Delta, South China: implications to regional sources

The Pearl River Delta (PRD) is one of the largest fast-developing economic zones in China. Hong Kong and the mainland part of the PRD differed in socio-economic development history and chemical management policies. Polyurethane foam (PUF)-passive air sampling (PAS) was deployed at 21 regional air quality monitoring stations across the PRD in summer and winter, respectively. Dichloro-diphenyl-trichloroethane (DDT), chlordane and hexachlorobenzene (HCB) were analyzed with GC-MS. High total DDT (240-3700 pg m(-3)) and chlordane (100-2600 pg m(-3)) concentrations were observed. Concentrations of DDTs and chlordane were higher in summer than winter; HCB vice versa. Spatially, the mainland part of the PRD generally displayed higher DDT concentrations than Hong Kong. Antifouling paint for fishing ships in coastal China was suggested to be an important current DDT source in the coast. The reason is unknown for the very low trans-/cis-chlordane (TC/CC) ratios (0.27) found in the mainland in winter. HCB concentrations were relatively uniform across the PRD, and long range transport of HCB from inland/North China to the PRD in winter was suggested.     

Geochemical fractionation of trace elements in sediments of Hugli River (Ganges) and Sundarban wetland (West Bengal, India)

A sequential extraction procedure was carried out to determinate the concentrations of 11 elements (Al, As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Zn) in different geochemical phases of sediments collected along the Hugli (Ganges) River Estuary and in the Sundarban mangrove wetland, eastern coastal part of India. The chemical speciation of elements was determined using the three-step sequential extraction procedure described by the European Community Bureau of Reference. Total metal concentration was determined using a microwave-assisted acid digestion procedure. Metal concentrations were near the background level except for As for which a moderate pollution can be hypothesized. The mobility order of the metals was: Cd?>?Mn?>?Cu?>?Zn?>?As?>?Co?>?Pb?>?Ni?>?Fe?>?Cr?>?Al. The highest percentage of Cd (>60%) was found in the most labile phase. Residual fraction was prevailing for Fe, Cr and Al, while Pb was mainly associated with the reducible fraction. Data were compared with Sediment Quality Guidelines to estimate the relationship between element concentrations and adverse biological effects on benthic community, finding the possibility of some toxic effects due to the presence of As in the entire studied area and Cd, only in Calcutta.     

The use of sensory perception indicators for improving the characterization and modelling of total petroleum hydrocarbon (TPH) grade in soils

This paper proposes a multistep approach for creating a 3D stochastic model of total petroleum hydrocarbon (TPH) grade in potentially polluted soils of a deactivated oil storage site by using chemical analysis results as primary or hard data and classes of sensory perception variables as secondary or soft data. First, the statistical relationship between the sensory perception variables (e.g. colour, odour and oil–water reaction) and TPH grade is analysed, after which the sensory perception variable exhibiting the highest correlation is selected (oil–water reaction in this case study). The probabilities of cells belonging to classes of oil–water reaction are then estimated for the entire soil volume using indicator kriging. Next, local histograms of TPH grade for each grid cell are computed, combining the probabilities of belonging to a specific sensory perception indicator class and conditional to the simulated values of TPH grade. Finally, simulated images of TPH grade are generated by using the P-field simulation algorithm, utilising the local histograms of TPH grade for each grid cell. The set of simulated TPH values allows several calculations to be performed, such as average values, local uncertainties and the probability of the TPH grade of the soil exceeding a specific threshold value.     

Variations of periphytic diatom sensitivity to the herbicide diuron and relation to species distribution in a contamination gradient: implications for biomonitoring

Diatoms are commonly used as bioindicators of trophic and saprobic pollution in rivers. However, more knowledge is needed concerning their sensitivity to toxicants such as agricultural herbicides. In this study, seven species of periphytic diatoms were isolated from the Morcille River (Beaujolais area, France) which presents a streamward contamination gradient by pesticides and particularly diuron. The sensitivity of these species to diuron was assessed through ecotoxicological tests based on short-term growth inhibition of monospecific cultures. After application of an appropriate toxicological model, EC50 were determined and the species were ranked according to their tolerance. EC50 values ranged from 4.5 to 19 μg L(-1). Finally, the results were related to field periphyton samples from an upstream and a downstream site in order to check if variations in specific relative abundance between sites are consistent with differences in tolerance to diuron. Species distribution between sites was only partially in accordance with toxicological results suggesting that other factors (toxic or trophic) have an important influence on diatom communities in the river. Nevertheless, diatoms showed their potential to indicate water contamination by pesticides and toxic indices could be developed in complement to existing trophic indices.     

PBDE,HBCD, and novel brominated flame retardant contamination in sediments from Lake Maggiore (Northern Italy)

The reduction in the use of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD) has opened the way for the introduction of novel brominated flame retardants (NBFRs) in place of the banned formulations. Important representatives of this group are decabromodiphenyl ethane (DBDPE), 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), hexabromobenzene (HBB), and pentabromoethylbenzene (PBEB). In this study, the contamination due to NBRFs was investigated for the first time in Italy in the sediments of Lake Maggiore. The aim of the research was to characterize in detail the possible presence of temporal trends and/or to identify potential sources of contamination. The study also considered the PBDE and HBCD lake sediment’s current contamination. The analytical results showed that sediments in Lake Maggiore and its tributary rivers had weak concentrations of PBEB, HBB, and BTBPE, but they did not have a negligible/insignificant contamination of HBCD (up to 23.7 ng/g dry weight (d.w.)). The determination of PBDEs in sediments showed that BDE-209 was the predominant congener (up to 217 and 28 ng/g d.w. in river and lake sediments, respectively). DBDPE was detected in the sediments with relevant concentrations (up to 280 ng/g d.w in the River Boesio sediments). The positive correlation of DBDPE with BDE-209 confirmed the wide and important use of this compound in the Lake Maggiore basin and the hypothesis that this compound will soon become one of the most important NBFRs used in Northern Italy. The contamination of Lake Maggiore sediments due to PBDEs, HBCD, and NBFRs were comparable to other worldwide situations.     

Determination of total petroleum hydrocarbons (TPH) in agricultural soils near a petrochemical complex in Guangzhou,China

The total petroleum hydrocarbons (TPH) pollution in regional agricultural soils was investigated. Seventy soil samples collected from surface layers (0–20 cm) and horizons of five selected pedons in the vicinity of a petrochemical complex in Guangzhou, China were analyzed, and the vertical variation and spatial variability of TPH were evaluated. The TPH concentration in top soils around the petrochemical complex ranged from 1,179.3 to 6,354.9 mg kg^− 1, with the average of 2,676.6 mg kg^− 1. Furthermore, significant differences between land-use types showed that the TPH concentration in top soils was strongly influenced by accidental spills. Both the TPH trends in pedons and the identified hot-spot areas also showed that the accidental explosions or burning accidents were mainly responsible for the pollution. The results reported here suggest that the regular monitoring and inspection shall be conducted for safety and to avoid or minimize the accidents, and the effective measures should be taken to remediate the contaminated areas and to assure that the important industrialization of Guangzhou area would not mean human health risks near the petrochemical complex.     

Some selected heavy metal concentrations in water,sediment, and oysters in the Er-Ren estuary,Taiwan: chemical fractions and the implications for biomonitoring

Studies of heavy metal contamination and ecological risk in estuaries are an important emerging area of environmental science. However, there have been few detailed studies of heavy metal contamination that concern the spatial variation of heavy metal levels in water, sediment, and oyster tissue. Because of the effective uptake of heavy metals, cultured oysters are a cheap and effective subject for study. This study, conducts an experiment in the Er-Ren river to examine the biological uptake of heavy metals in farmed, cultured oysters. The distribution of copper, zinc, lead, cadmium, and arsenic concentrations in water, sediment, and oysters from the Er-Ren river is also evaluated. By sequential extraction of the sediments, the following order of mobilities is found for heavy metals Pb?>?Cd?>?As?>?Zn?>?Cu. The highest percentages of heavy metals are found in the residual phase. The mean uptake rates for young oysters are 7.24 mg kg^?1 day^?1 for Cu and 94.52 mg kg^?1 day^?1 for Zn, but that for adult oyster is 10.79 mg kg^?1 day^?1 for Cu and 137.24 mg kg^?1 day^?1 for Zn. With good policies and management, the establishment of cultured oyster frames in these contaminated tributaries and near shore environments is a potential method for removing Cu and Zn and protecting the coast.     

Monitoring of copper,arsenic and antimony levels in agricultural soils impacted and non-impacted by mining activities,from three regions in Chile

This paper reports a comparative study of the concentration of three important environmental elements that are often found together in mineral deposits and then associated with mining activities; copper, arsenic and antimony. These elements were determined in 26 different agricultural soils from regions I, II and V in Chile, zones where the most important and biggest copper industries of this country are located. As background levels of these elements in soils have not been well established, in this study, both, impacted and non-impacted agricultural soils from different regions were considered. The relationships between the concentrations of these elements in soils were also examined. The concentration ranges for copper, arsenic and antimony were 11-530; 2.7-202 and 0.42-11 mg kg(-1) respectively. The copper concentrations in non-polluted soils from the north and central zone of Chile were similar. However, three sites from the north region have copper concentration as higher as 100 mg kg(-1), values that exceed the critical concentration for copper in soils. The concentration of arsenic and antimony in the north soils were higher than in non-impacted ones and, in the case of arsenic, greatly exceeded the world average concentration reported for this element in soils. The highest arsenic and antimony concentrations were found in Calama and Quillagua soils, two different sites in the Loa valley. The arsenic/antimony concentration ratio was higher in Quillagua soil. The high concentrations of three elements determined in impacted soils from region V (Puchuncaví and Catemu valleys) clearly shows the impact produced in this zone by the industrial and mining activities developed in their proximities. At Puchuncaví valley a clear decrease was observed in copper, arsenic and antimony concentrations in soils on the function of the distance from the industrial complex "Las Ventanas", and all concentrations exceeded the reported critical values for this matrix. Instead at Catemu valley, only the copper concentration was higher than this value. Statistically significant correlation was found for Cu-Sb in all soils; more significant Cu-As, Cu-Sb and Sb-As correlations were evaluated for soils from Puchuncaví and Catemu valleys, corroborating that high concentrations of copper, arsenic and antimony in these soils coming from the same pollution sources, the copper industry and the thermoelectric power plant.     

Spatial variability and temporal changes in the trace metal content of soils: implications for mine restoration plan

Trace metals in soils may be inherited from the parent materials or added to the system due to anthropogenic activities. In proposed mining areas, trace metals become an integral part of the soil system. Usually, researchers undertake experiments on plant species selection (for the restoration plan) only after the termination of mining activities, i.e. without any pre-mining information about the soil-plant interactions. Though not shown in studies, it is clear that several recovery plans remain unsuccessful while carrying out restoration experiments. Therefore, we hypothesize that to restore the area effectively, it is imperative to consider the pre-mining scenario of metal levels in parent material as well as the vegetation ecology of the region. With these specifics, we examined the concentrations of trace metals in parent soils at three proposed bauxite locations in the Eastern Ghats, India, and compared them at a spatio-temporal scale. Vegetation quantification and other basic soil parameters accounted for establishing the connection between soil and plants. The study recorded significant spatial heterogeneity in trace metal concentrations and the role of vegetation on metal availability. Oxidation reduction potential (ORP), pH and cation exchange capacity (CEC) directly influenced metal content, and Cu and Ni were lithogenic in origin. It implies that for effective restoration plant species varies for each geological location.