Spatial variation of potentially toxic elements in different grain size fractions of marine sediments from Gulf of Mannar, India

Marine sediments of the Gulf of Mannar (GoM), India are contaminated by potential toxic elements (PTEs) due to anthropogenic activities posing a risk to the existing fragile coral ecosystem and human health. The current study aimed to assess the distribution of PTEs (arsenic—As; cobalt—Co; copper—Cu, molybdenum—Mo; lead—Pb; and zinc—Zn) in marine sediments of different grain size fractions, viz., medium sand (710 μm), fine sand (250 μm), and clay (<63 μm) among the different coastal regions of Pamban, Palk Bay, and Rameswaram coasts of GoM, using grain size as one of the key factor controlling their concentrations. The concentrations of PTEs were measured in the different size fractions of sediment using inductively coupled plasma mass spectrophotometer. The order of accumulation of all PTEs in the three fractions was ranked as Zn > Cu > Pb > As > Co > Mo and in the three locations as Rameswaram > Palk Bay > Pamban. The concentration of PTEs in Palk Bay and Rameswaram coast was significantly different (P?<?0.05), when compared to Pamban coast. Measured geoaccumulation index (I _geo) and contamination factor (CF) indicated significant enrichment of Co and Pb from Rameswaram coast when compared to other two coasts. Although the concentration of Co was low but the measured I _geo and CF values indicated significant enrichment of this PTE in Rameswaram coast. The increased input of PTEs in the coastal regions of GoM signifies the need to monitor the coast regularly using suitable monitoring tools such as sediments to prevent further damage to the marine ecosystem.     

Heavy metal concentrations in water, suspended matter, and sediment from Gökova Bay, Turkey

The contents of heavy metals (Fe, Mn, Pb, Cu, Cd, and Hg) dissolved in water and suspended solids of Gökova Bay—partly and fully sampled in 2005 and 2006, respectively—are quite higher than the average values encountered in uncontaminated sea water. The high concentrations are associated with terrestrial inputs from the mining zones and anthropogenic (domestic + industrial) sources. Moreover, the distribution of Fe and Cu is affected by primary production because these elements function as nutrients in biological activities. The Cr, Ni, and Fe concentrations of surface sediments are above the shale average. The Cr and Ni contents of surface sediments representative of river mouths strongly correlate with total phosphorus contents. In a sulfide-poor environment, Pb and Cu were concentrated at a higher ratio in surface sediments than Cd, probably due to higher stabilities of their surface complexes with amorphous iron oxides and clay minerals existing as major components in the sediments. The exceptional enrichment of Zn may be attributed to double oxide formation with amorphous iron oxides in sediments. The high metal values are most probably caused by terrestrial inputs from anthropogenic sources and the mining zones at the southeast part of the bay. The Al, Mn, Pb, Cu, Zn, and Hg contents are below the shale average. The low values have possibly originated from the coarse-grained sandy sediments having a low affinity for metals. There are no distinct differences in the metal distributions in water and suspended matter between the years 2005 and 2006 in the bay, probably due to low sedimentation rates.     

Assessment of trace metal pollution in surface sediments of Nemrut Bay, Aegean Sea

Surface sediments collected from nine stations in Nemrut Bay, Aegean Sea were analyzed for trace metals (Hg, Cd, Pb, Cr, Cu, Zn, Mn, Ni, Fe, As, and Mg) and grain sizes. The results were compared with the numerical sediment guidelines used in North America as well as literature values reported for similar studies conducted in Izmit Bay and Izmir Bay. The metal levels were also evaluated according to the enrichment factor and contamination factor analyses. The analyses revealed significant anthropogenic pollution of Hg, Pb, Zn, and As in the surficial sediments of Nemrut Bay.     

Assessment of heavy metal contamination in Candarli Gulf sediment, Eastern Aegean Sea

Concentrations of selected heavy metals (Fe, Mn, Ni, Cu, Zn, Pb, Hg, Cr, Al, and As) in surface sediments from 18 stations in the Candarli Gulf were studied in order to understand current metal contamination due to urbanization and economic development in Candarli region, Turkey. The sediment samples were collected by box corer in Candarli Gulf in 2009 to assess heavy metal pollution. Heavy metal concentrations in surface sediment varied from 1.62% to 3.60% for Fe, 0.38?C2.53% for Al, 173?C1,423 for Mn, 8?C100 for Ni, 3?C46 for Cu, 55?C119 for Zn, 16?C138 for Pb, 0.2?C6.3 for Hg, 16?C71 for Cr, and 11?C37 mg kg^???1 for As. This study showed that the concentrations of Mn, Ni, Zn, Pb, Hg, and Cr in the surface sediment layers were elevated when compared with the subsurface layers. Both metal enrichment and contamination factors show that Hg, Zn, and Pb contamination exists in the entire study area and contamination of other metals is also present in some locations depending on the sources.     

<Emphasis Type="Italic">Mazzaella laminarioides</Emphasis> and <Emphasis Type="Italic">Sarcothalia crispata</Emphasis> as possible bioindicators of heavy metal contamination in the marine coastal zone of Chile

The suitability of Mazzaella laminarioides and Sarcothalia crispata as heavy metal biomonitors of Cd, Cu, Hg, Pb, and Zn was assessed by comparing bioaccumulation of these elements in different life stages and frond sizes in samples from three locations, San Vicente Bay (industrial area), Coliumo, and Quidico (the latter as a reference station), where different degrees of heavy metal pollution are recorded. Bioaccumulation and bioconcentration factors of Cd, Cu, Hg, Pb, and Zn were evaluated. The two macroalgae species showed similar patterns, with higher values of Cu, Hg, Pb, and Zn in polluted areas. M. laminarioides bioaccumulated higher concentrations of all metals assessed than S. crispata, independent of life stage and frond size. The results also showed significantly higher Cu, Hg, Pb, and Zn concentrations (p < 0.05) in water samples from San Vicente Bay than those measured in Coliumo and Quidico. Concentrations of Cd, Hg, Pb, and Zn in San Vicente Bay and Cd, Hg, and Pb in Coliumo and Quidico exceed the mean values considered to represent natural concentrations (Cu = 3.00 μg L^?1; Zn = 5.00 μg L^?1; Pb = 0.03 μg L^?1; Cd = 0.05 μg L^?1; Hg = 0.05 μg L^?1); however, the concentrations recorded do not cause negative effects on the growth and survival of macroalgae. The assessment of heavy metals bioaccumulated in M. laminarioides and S. crispata, particularly Hg, Pb, and Zn, offers a reliable approach for pollution assessment in rocky intertidal environments. Cu and Cd concentrations in seawater samples from San Vicente and Coliumo Bays were significantly higher than in those from Quidico (p value < 0.05); no significant differences in Cd concentrations were observed between San Vicente and Coliumo Bays (p < 0.05). Exceptionally, Cd is bioaccumulated at high levels independent of its availability in the water, thus reaching high concentrations in control areas. High concentrations of metals like Cu and Zn may limit or inhibit Cd uptake in macroalgae, since the transport channels are saturated by some metals, reducing the accumulation of others. These macroalgae species offer good potential for the development of suitable heavy metal pollution survey tools in rocky intertidal environments.     

Heavy metal in surface sediments of the Liaodong Bay, Bohai Sea: distribution, contamination, and sources

In an effort to assess the potential contamination and determine the environmental risks associated with heavy metals, the surface sediments in Liaodong Bay, northeast China, were systematically sampled and analyzed for the concentrations of Cu, Pb, Zn, Cr, Ni, As, and Hg. The metal enrichment factor (EF) and geoaccumulation index (I _geo) were calculated to assess the anthropogenic contamination in the region. Results showed that heavy metal concentrations in the sediments generally met the criteria of China Marine Sediment Quality (GB18668-2002); however, both EF and I _geo values suggested the elevation of Pb concentration in the region. Based on the effect-range classification (TEL-PEL SQGs), Cu, Pb, Ni, and As were likely to pose environment risks, and the toxic units decreased in the order: Ni?>?Pb?>?Cr?>?Zn?>?As?>?Cu?>?Hg. The spatial distribution of ecotoxicological index (mean-ERM-quotient) suggested that most of the surface sediments were “low–medium” priority zone. Multivariate analysis indicated that the sources of Cr, Ni, Zn, Cu, and Hg resulted primarily from parent rocks, and Pb or As were mainly attributed to anthropogenic sources. The results of this study would provide a useful aid for sustainable marine management in the region.     

Metal contents in coastal waters of San Jorge Bay, Antofagasta, northern Chile: a base line for establishing seawater quality guidelines

We measured the concentration of 12 metals in coastal waters of seven sites of San Jorge Bay in Antofagasta (northern Chile), in order to relate the presence of metals with the different uses of San Jorge Bay coastal border, and to evaluate the quality of the bay's bodies of water according to the proposed current Chilean Quality Guide for trace elements in seawater (CONAMA 2003). The results suggest that the coastal water of San Jorge Bay has very good quality according to the proposed regulation mentioned above. However, the distribution of metals such as Cu and Pb along the bay's coast line evidences a notorious effect of the industrial activity, which would involve different behavior patterns for some trace elements in some bodies of water, suggesting that the levels indicated in the environmental guideline of the Chilean legislation do not represent pollution-free environments.     

Impact of anthropogenic input on physicochemical parameters and trace metals in marine surface sediments of Bay of Bengal off Chennai, India

The study of heavy metal distribution in coastal surface sediments is an important component in understanding the exogenic cycling as well as in assessing the effect of anthropogenic influences on the marine ecosystem. In this study, surface sediment samples were collected from five different traverses along the innershelf of Bay of Bengal, off Chennai, India during pre- and post-monsoon seasons. The results of Spearmen correlation matrix, factor and cluster analysis, enrichment and contamination factor analysis, and geoaccumulation index of the heavy metals analyzed in the collected surface sediment were discussed. The level of both enrichment and contamination factor are shown in following order Cd > Cu > Cr > Ni > Pb > Co > Zn > Mn > Fe > Hg. The geoaccumulation index suggests that Cd and Cu are strongly to extremely pollute the sediments in both seasons. The results strongly indict anthropogenic sources for moderate input of Cd and Cu in to the innershelf of Chennai coast.     

Effect of heavy metals (Cu, Pb, and As) on the ultrastructure of Sargassum pallidum in Daya Bay, China

Concentrations of Cu, Pb, and As were determined in seawater, surface sediment, Sargassum pallidum collected from the Daya Bay, China. The influence of metal contamination on the marine alga was investigated at chemical and ultrastructural level. Mean concentrations of Cu (19.44 mg kg^?1) and Pb (33.99 mg kg^?1) were found to be high in sediment, whereas concentration of As (122.29 mg kg^?1) in S. pallidum was higher than that in water and sediment. The ultrastructure of S. pallidum cells was anomalous and aberrant. Energy-dispersive x-ray spectroscopic analysis revealed that the nanometal particles in the form of comparatively high-electron density substance diffused in the cell structures constituted by Cu, Pb, As, etc. There is a remarkable similarity or correspondence in the anomalous elements between the geochemistry and the botanic cell, and the heavy metals have potential hazardous effect on the ocean ecology system in Daya Bay.     

Characterization of land-based sources of pollution in Jobos Bay,Puerto Rico: status of heavy metal concentration in bed sediment

As part of an assessment of land-based sources of pollution in Jobos Bay, Puerto Rico, sediment samples were collected at 43 sites to characterize concentrations of a suite of pollutants, including metals. Fifteen major and trace metals (Ag, Al, As, Cd, Cr, Cu, Fe, Hg, Mn Ni, Pb, Sb, Se, Sn, and Zn) were measured along with total organic carbon and grain size in surficial sediments. For most metals, maximum concentrations were seen in the eastern bay; however, values were still within concentration ranges found in other estuarine systems. In contrast, silver was higher in the western region. In general, metal distribution in the bay was positively correlated with grain size. Additionally, correlations between Al and other metals suggest natural sources for metals. The data presented here suggest that, although the Jobos Bay watershed contains both urban centers along with industrial and agricultural developments, anthropogenic inputs of metals may be negligible.     

Contamination and ecological risk assessment of toxic trace elements in the Xi River, an urban river of Shenyang city, China

The objectives of this study were to assess the enrichment, contamination, and ecological risk posed by toxic trace elements in the sediments of the Xi River in the industrialized city of Shenyang, China. Surface sediment and sediment core were collected; analyzed for toxic trace elements; and assessed with an index of geoaccumulation (Igeo), enrichment factor (EF) value, potential ecological risk factor (Er), ecological risk index (RI), and probable effect concentration quotient (PECQ). Elemental concentrations (milligram per kilogram) were 8.5–637.9 for As, 6.5–103.9 for Cd, 12.2–21.9 for Co, 90.6–516.0 for Cr, 258.1–1,791.5 for Cu, 2.6–19.0 for Hg, 70.5–174.5 for Ni, 126.9–1,405.8 for Pb, 3.7–260.0 for Sb, 38.4–100.4 for V, and 503–4,929 for Zn. The Igeo, EF, Er, and PECQ indices showed that the contamination of Cd and Hg was more serious than that of As, Cr, Cu, Ni, Pb, Sb, and Zn, whereas the presence of Co and V might be primarily from natural sources. The Igeo index for Cr and Ni might underestimate the degree of contamination, potentially as a result of high concentrations of these elements in the shale. The RI index was higher than 600, indicating a notably high ecological risk of sediment for the river. The average PECQ for As, Cd, Cr, Cu, Hg, Ni, Pb, and Zn ranged from 1.4 to 4.1 for surface sediment and from 5.2 to 9.6 in the sediment cores, indicating a high potential for an adverse biological effect. It was concluded that the sediment in the Xi River was severely contaminated and should be remediated as a hazardous material.     

Source identification and assessment of sediment contamination of trace metals in Kogarah Bay,NSW, Australia

The distribution of trace metals (spatial and temporal) and sedimentary fractions were investigated to identify the concentrations and sources of trace metals within Kogarah Bay, NSW, Australia. A total of 59 surface sediments and six subsurface samples from core of the sediment were collected. The contamination factor and pollution load index indices used to evaluate environmental effects of trace metals. The study area was found to be uncontaminated with Cr and Ni, moderately contaminated with As and considerably contaminated with Cu, Zn and Pb. The concentrations of Cr and Ni were below both effect range low and effect range median, while As, Cu, Zn and Pb were slightly above effect range low. The highest concentrations of these trace metals such as Cu, Zn and Pb were found in the north, northwest and southeast of the bay, close to discharge points, stormwater outlets and around boatyards and watercrafts. The spatial distributions of metals were strongly related to muddy particles and organic matter. The temporal sediments of metals declined with increased sediment depth, which reflects accumulation of trace metals since European settlement in this area. Furthermore, the source of the trace metals was found to be stormwater outlets, gasoline fumes, boatyards and other human activities.     

Enhanced anthropogenic heavy metal dispersal from tidal disturbance in the Jiaozhou Bay, North China

Heavy metal contamination in surface sediments of the Jiaozhou Bay was investigated in this study. Sediment sample was collected from the Jiaozhou Bay and its rivers. Heavy metal concentration was determined by inductively coupled plasma atomic emission spectroscopy and graphite furnace atomic absorption spectrometry. The result shows that river sediment in the east coast of the Jiaozhou Bay was heavily polluted especially for the Cu, Pb, Cd, and Zn. A slightly increase of heavy metal concentration was observed at stations near the east coast in the Jiaozhou Bay; however, contaminated sediment from polluted river was constrained mostly near shore within 3–4 km. Downstream decrease of heavy metals in river mouth suggested dilution from strong tidal current. Rapid seaward decline in the east coast and alongshore band dispersal pattern of heavy metals in surface sediment indicated mixing and remobilizing enhanced by large tidal range that regulated dispersal of sediments and anthropogenic heavy metals in the Jiaozhou Bay area.     

Using public participation to sample trace metals in lake surface sediments: the OPAL Metals Survey

Members of the public in England were invited in 2010 to take part in a national metals survey, by collecting samples of littoral sediment from a standing water body for geochemical analysis. To our knowledge, this is the first national sediment metals survey using public participation and reveals a snapshot of the extent of metals contamination in ponds and lakes across England. Hg, Ni, Cu, Zn and Pb concentrations exceeding sediment quality guidelines for the health of aquatic biota are ubiquitous in ponds and lakes, not just in areas with a legacy of industrial activity. To validate the public sampling approach, a calibration exercise was conducted at ten water bodies selected to represent a range of lakes found across England. Sediment concentrations of Hg, Ni, Cu, Zn and Pb were measured in samples of soil, stream and littoral and deep water sediment to assess inputs. Significant differences between littoral sediment metal concentrations occur due to local variability, but also organic content, especially in upland, peat soil catchments. Variability of metal concentrations between littoral samples is shown to be low in small (<20 ha) lowland lakes. Larger and upland lakes with more complex inputs and variation in organic content of littoral samples have a greater variability. Collection of littoral sediments in small lakes and ponds, with or without voluntary participation, can provide a reliable sampling technique for the preliminary assessment of metal contamination in standing waters. However, the heterogeneity of geology, soils and history/extent of metal contamination in the English landscape, combined with the random nature of sample collection, shows that systematic sampling for evaluating the full extent of metal contamination in lakes is still required.     

Distribution and baseline values of trace elements in the sediment of Var River catchment,southeast France

This study reports on the determination of trace element (TE)—Li, As, Co, Cs, Cu, Pb, U, and Zn—and major element (ME)—Si, Al, Fe, Mg, Ca, Mn, Na, and K—concentrations in 18 riverbed sediments and a sediment core from the Var River catchment using inductively coupled plasma mass spectrometry (ICP-MS). The results were compared with those of a reference sediment core, and the contribution of clay and organic carbon contents in the distribution of TE and ME in the sediment samples was investigated. The mean concentrations of the ME were comparable in both core and riverbed samples and were within the natural averages. In the case of TE, the concentrations were lower in riverbed sediment samples than those found in the sediment core. High mean concentration of As was observed (7.6 μg g^?1) in both core and riverbed sediments, relatively higher than the worldwide reported values. The obtained data indicated that the natural high level of arsenic might be originated from the parent rocks, especially metamorphic rocks surrounding granites and from Permian sediments. Statistical approach, viz., Pearson correlation matrix, was applied to better understand the correlation among TE in both riverbed and sediment core samples. No significant metallic contamination was detected in the low Var valley despite of the localization of several industrial facilities. Therefore, results confirm that the concentrations of the TE obtained in the riverbed sediments could be considered as a baseline guide for future pollution monitoring program.     

Assessment of heavy metal levels in sediment samples of Kapulukaya Dam Lake (Kirikkale) and lower catchment area

In this study, the concentrations of 13 elements (Al, Fe, Mn, Cr, Ni, Zn, Co, As, Pb, Cu, Mo, Hg, and Cd) were determined in the sediments of three different sites in the Kapulukaya Dam Lake between May 2007 and November 2008. They ranged from 1.47 to 4.64 for Al, 0.92 to 3.48 for Fe (in percent), 326.60 to 1053.00 for Mn, 98.00 to 1,116.00 for Cr, 24.70 to 127.10 for Ni, 14.80 to 124.20 for Zn, 11.0 to 43.20 for Co, 5.00 to 29.30 for Cu, 9.10 to 69.70 for As, 8.60 to 34.00 for Pb, 2.50 to 5.20 for Mo, 1.00 to 1.60 for Hg, and 0.50 to1.80 for Cd in microgram per gram dry weight sediment. The contamination degree of the sediment was assessed on the basis of enrichment factor and corresponding sediment quality guideline. The calculated enrichment factors (EF, measured metal vs. background concentrations) indicated that the effect of man-made activities on the occurrence of concentrations could be accounted for the majority of heavy metals namely Mn, As, Ni, Cu, Zn, Cr, Co, Mo, and Cd, whereas such affect was not detected for Hg and Pb. The maximum values of the EF were represented by As, minimum values by Hg at all sites. Mean EF values were 36.60 and 0.70 for As and Hg, respectively. This study has clearly assessed a certain level of heavy metal pollution in the region, based particularly on the findings from sediment.     

The impact of an industrial complex on freshly deposited sediments, Chener Rahdar river case study, Shiraz, Iran

Concentrations of elements (As, Co, Cu, Ni, Mo, Pb, V, and Zn) are studied in the sediments of two adjacent stretches of Chenar Rahdar river. The first stretch (S1) is influenced by urban and arable land wastewater, and the second (S2) is mainly loaded with industrial effluents. The average abundance order of heavy metals content in S1 sediments is Ni > V > Zn > Cu > Co > As > Pb > Mo and in S2 sediments is Ni > Zn > V > Cu > Mo > Pb > Co > As. The maximum average concentration for these heavy metals (except for As) occurs in the S2 sediments. The contamination factor (CF) base of background in S1 for eight analyzed elements is moderate. The CF for Cu, Zn, and Pb in S2 sediments is considerable. The highest CF in S1 and S2 sediments is observed for Mo (CF = 10.95 and 12.41) and indicates very high contamination. The application of modified degree of contamination values (mC_d) indicates low and high degree of contamination (1.89–4.15) in S1 and S2, respectively. Calculated enrichment factors (EF) reveal enrichment of Mo and As in S1 and Zn, Cu, Mo, and Pb in S2 compared to the average abundances of background level. The maximum EF for Mo is 7.61 (significant enrichment), while Pb, Zn, and Cu with maximum EF between 2 and 5 indicate moderate contamination. Principal component analysis (PCA) shows distinctly different elemental associations in S1 and S2 sediments. The strong association of Zn, Co, Ni, Sc, Cu, Al and Fe in S1 suggests a similar source. The results of PCA for Zn, Pb, Mo and Cu in S2 (componente2) indicate that these metals are influenced by anthropogenic activity. Also, high loading heavy metals with OC (0.97) indicate that organic carbon plays a significant role in the distribution and sorption of these heavy metals in the sediments. Factor analysis indicates that As and Mo behave differently in sediment samples.     

Assessment of farmland sediments after flooding in Ubeji Land in Niger Delta of Nigeria

A study was conducted to evaluate ten heavy metals in dry sediment samples used to assess the contamination of farmland in Niger Delta after a protracted flooding. Eighteen sediment samples in six locations were collected. Niger Delta is a major industrial area where Nigeria petrochemical company is located. These sediments were subjected to analysis using standard methods for the examination of the soil samples. Results showed a trend toward induction of environmental contamination with Zn, Cu, Fe, Hg and Pb on the farmland. Mercury and Lead are disproportionately higher than other sediment elements. Concentrations of these sediment elements are above compliance limit for Nigeria and these may have long-term adverse effects on soil and vegetation.     

Impact of poor solid waste management on ground water

Eight sediment cores recovered from Tamaki Estuary were analysed for Cu, Pb, Zn, and Cd using downward cored sub-samples. The results indicate a significant upward enrichment in heavy metals with the highest concentrations found in the uppermost 0–10 cm layer. Assessment of heavy metal pollution in marine sediments requires knowledge of pre-anthropogenic metal concentrations to act as a reference against which measured values can be compared. Pristine values for the cored sediments were determined from flat “base-line” metal trends evident in lower core samples. Various methods for calculating metal enrichment and contamination factors are reviewed in detail and a modified and more robust version of the procedure for calculating the degree of contamination is proposed. The revised procedure allows the incorporation of a flexible range of pollutants, including various organic species, and the degree of contamination is expressed as an average ratio rather than an absolute summation number. Comparative data for normalized enrichment factors and the modified degree of contamination show that Tamaki Estuary sediments have suffered significant systematic heavy metal contamination following catchment urbanization. Compared to baseline values the uppermost sediment layers show four-fold enrichment averaged across eight cores and four analysed metals.     

Spatial distribution and concentration assessment of total petroleum hydrocarbons in the intertidal zone surface sediment of Todos os Santos Bay, Brazil

The primary objective of this study was to investigate the concentrations and spatial distribution of the total petroleum hydrocarbons (TPHs) in the intertidal zone surface sediment of Todos os Santos Bay, Brazil, to assess the distribution and degree of contamination by TPHs, measure the level of TPH degradation in the surface sediment, and identify the organic matter sources. The surface sediment used in this study was collected in 50 stations, and TPHs, isoprenoid alkanes (pristane and phytane), and unresolved complex mixture (UCM) were analyzed by gas chromatography with a flame ionization detector. The total concentrations ranged from 0.22 to 40,101 μg g^?1 dry weight and showed a strong correlation with the total organic carbon (TOC) content. The highest TPH concentrations were observed in samples from the mangrove sediments of a river located near a petroleum refinery. Compared with other studies in the world, the TPH concentrations in the intertidal surface sediment of Todos os Santos Bay were below average in certain stations and above average in others. An analysis of the magnitude of UCM (0.11 to 17,323 μg g^?1 dry weight) and the ratios nC17/Pr and nC18/Ph suggest that an advanced state of oil weathering, which indicates previous contamination. The molar C/N ratios varied between 5 and 43, which indicate organic matter with a mixed origin comprising marine and continental contributions.