Seasonal, spatial and inter-annual variations of trace metals in mussels from the Adriatic sea: a regional gradient for arsenic and implications for monitoring the impact of off-shore activities

Mussels are widely used as bioindicator organisms for monitoring chemical pollutants including trace metals. These elements are natural constituents in the marine environment and their basal concentrations in the organisms can be influenced by several environmental and biological factors. The aim of this work was to extend our knowledge on the natural variability of trace metals in mussels tissues, focusing on seasonal and inter-annual fluctuations in a coastal reference site of the Adriatic coast (Portonovo); a total of 39 samplings were performed during 5 years, providing an extended data-set for tissue levels of As, Ba, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Se, V and Zn. Concentrations of trace metals in mussels tissues revealed marked seasonal fluctuations with significant differences between various sampling years. Such fluctuations appeared mostly related to phytoplanctonic blooms and especially to reproductive cycle which exhibited a certain inter-annual shift of the gametogenesis period. Lower concentrations were measured in summer months for the majority of elements while a different seasonal cycle was observed for arsenic, not correlated with gonadic development, neither with other elements. Chemical speciation of arsenic was characterized to distinguish compounds of natural origin from those potentially reflecting an anthropogenic impact. Arsenobetaine and arsenocholine were always the predominant forms (up to 85% of total arsenic), while a significant increase of dimethylarsine and trimethylarsine oxide in spring (24% of total arsenic) might reflect the effect of phytoplanctonic bloom on both geochemistry and trophic transfer of this element. A significant inter-annual variability was observed for both the seasonal cycle and the range of values measured for all the elements, with particularly marked differences for arsenic, ranging from less than 10 to more than 40 microg/g in summer periods of different years. Data obtained on reference mussels were used to assess the impact of 41 off-shore platforms distributed along 5 nautical districts in the Northern and Central Adriatic Sea. Organisms sampled on these structures from 2001 to 2005 exhibited a certain enrichment of cadmium and zinc, probably associated to the use of anodic electrodes. Marked annual and geographical variations were measured for concentrations of arsenic in mussels of different platforms. However, the comparison with results of Portonovo, allowed to exclude the anthropogenic impact of exploitation activities and revealed a natural regional gradient of arsenic levels in mussels tissues associated to the changing influence of the Po river runoff on seawater salinity. In particular the higher concentrations measured in organisms sampled from platforms in the Central compared to Northern Adriatic confirmed a significant relationship between salinity and arsenic bioaccumulation, consistent with a role of arsenobetaine as an acquired osmolyte for mussels. The overall results confirmed the importance of natural variability when assessing the potential impact of anthropogenic activities.     

Trace metals in arcid clam Scapharca inaequivalvis: effects of molluscan extracts on bioluminescent bacteria

The relationship between a supposed effect of molluscan extracts on bioluminescent bacteria and metal concentrations in the extracts was investigated. For this purpose a biotoxicological assay based on bioluminescent bacteria (BLB) and extracts from metal exposed molluscs, Scapharca inaequivalvis, was optimized to monitor Cd and Cu marine pollution. Cu and Cd concentrations increased in tissues of experimentally exposed molluscs. Molluscan extracts inhibited the bacterial luminescence, the inhibition decreasing as the time of mollusc exposure to metals increased, suggesting a reduction of the "bioactive" metals. In regard to the use of BLB test in environmental monitoring, the analysis of Cu, Cd, and metallothionein (MT) was first performed in tissues from molluscs collected in three different areas of Northern Adriatic Sea. Metal concentrations reached maximum values in the gills, while Cd was mostly bound to MT in the kidney. Significant differences in metals and MT concentrations were found depending on the sampling sites. The biotoxicological assay resulted slightly correlated with the biochemical parameters.     

Modeling the influence of climate change on the mass balance of polychlorinated biphenyls in the Adriatic Sea

Climate forcing is forecasted to influence the Adriatic Sea region in a variety of ways, including increasing temperature, and affecting wind speeds, marine currents, precipitation and water salinity. The Adriatic Sea is intensively developed with agriculture, industry, and port activities that introduce pollutants to the environment. Here, we developed and applied a Level III fugacity model for the Adriatic Sea to estimate the current mass balance of polychlorinated biphenyls in the Sea, and to examine the effects of a climate change scenario on the distribution of these pollutants. The model’s performance was evaluated for three PCB congeners against measured concentrations in the region using environmental parameters estimated from the 20th century climate scenario described in the Special Report on Emission Scenarios (SRES) by the IPCC, and using Monte Carlo uncertainty analysis. We find that modeled fugacities of PCBs in air, water and sediment of the Adriatic are in good agreement with observations. The model indicates that PCBs in the Adriatic Sea are closely coupled with the atmosphere, which acts as a net source to the water column. We used model experiments to assess the influence of changes in temperature, wind speed, precipitation, marine currents, particulate organic carbon and air inflow concentrations forecast in the IPCC A1B climate change scenario on the mass balance of PCBs in the Sea. Assuming an identical PCBs’ emission profile (e.g. use pattern, treatment/disposal of stockpiles, mode of entry), modeled fugacities of PCBs in the Adriatic Sea under the A1B climate scenario are higher because higher temperatures reduce the fugacity capacity of air, water and sediments, and because diffusive sources to the air are stronger.     

Seasonal and spatial patterns of metals at a restored copper mine site. I. Stream copper and zinc

Seasonal and spatial variations in metal concentrations and pH were found in a stream at a restored copper mine site located near a massive sulfide deposit in the Foothill copper-zinc belt of the Sierra Nevada, California. At the mouth of the stream, copper concentrations increased and pH decreased with increased streamflow after the onset of winter rain and, unexpectedly, reached extreme values 1 or 2 months after peaks in the seasonal hydrographs. In contrast, aqueous zinc and sulfate concentrations were highest during low-flow periods. Spatial variation was assessed in 400 m of reach encompassing an acidic, metal-laden seep. At this seep, pH remained low (2-3) throughout the year, and copper concentrations were highest. In contrast, the zinc concentrations increased with downstream distance. These spatial patterns were caused by immobilization of copper by hydrous ferric oxides in benthic sediments, coupled with increasing downstream supply of zinc from groundwater seepage.     

Seasonal variations of selected herbicides and related metabolites in water, sediment, seaweed and clams in the Sacca di Goro coastal lagoon (Northern Adriatic)

This study assesses the status of Sacca di Goro coastal lagoon (Northern Adriatic, Italy) with respect to watershed pollution. Because 80% of its watershed is devoted to agriculture, plant protection products and their metabolites were found in the water column, sediments (the upper 0-15 cm layer), macroalgae (Ulva rigida) and clams (Tapes philippinarum). Five seasonal sampling campaigns were performed from May 2004 to April 2005 and concentrations measured in five stations in the lagoon and six in the watershed. Relatively high concentrations of the s-triazine - terbuthylazine -, urea herbicides - diuron - and alachlor were detected through the year mainly at stations directly influenced by the Po di Volano inflow. The concentrations of products in use follow a clear seasonal pattern with spring peaks. This pattern is also visible in the sediments as well as in biota. Among metabolites, hydroxylated compounds prevailed, often with concentrations greater than those of the parent compounds. For the most part of the year, the concentrations in biota were close to detection limits, with concentration peaks in spring.     

Distribution of heavy metals in muscle, liver and kidney of northern fur seal (Callorhinus ursinus) caught off Sanriku, Japan and from the Pribilof Islands, Alaska

The concentrations of iron, manganese, zinc, copper, cadmium, and mercury were determined in muscle, liver and kidney of 67 northern fur seals (Callorhinus ursinus) collected off Sanriku, Japan, and from the Pribilof Islands, Alaska. Almost all the elements except cadmium were highest in liver. Cadmium levels in kidney were higher than those in liver and muscle for all animals analyzed. Concentrations of mercury increased significantly with age in muscle, liver and kidney, as did iron levels in muscle and liver and cadmium levels in muscle, while manganese concentrations decreased with age in muscle and kidney. The kidney also showed decreased copper concentration with age. Cadmium concentrations of the northern fur seals in this study were higher than the other otariids, reflecting a predominantly squid diet. Concentrations of manganese and mercury were found to be higher in the fur seals caught off Sanriku than in animals from the Pribilof Islands, while those of zinc and cadmium were found to be lower. Variable concentrations of cadmium might have been attributed to those in seawaters. Discriminant analysis of heavy metal concentrations was used to identify habitat. Sixty-three of 67 animals (94%) were correctly classified using this technique. Heavy-metal concentrations in tissues may provide a useful method to elucidate the primary feeding grounds of fur seals.     

Seasonal variations of hydroxylated and methoxylated brominated diphenyl ethers in blue mussels from the Baltic Sea

Hydroxylated polybrominated diphenyl ethers (OH-PBDEs) and methoxylated polybrominated diphenyl ethers (MeO-PBDEs) found at high levels in the Baltic biota are mainly natural products, but can also be formed through metabolism or abiotic oxidation of polybrominated diphenyl ethers (PBDEs). The formation of OH-PBDEs is of concern since there is growing evidence of phenolic toxicity. This study investigates seasonal variations in levels of OH-PBDEs and MeO-PBDEs, focusing on an exposed species, the blue mussel (Mytilus edulis), sampled in the Baltic Sea in May, June, August and October of 2008. Both the OH-PBDE and MeO-PBDE levels in the mussels showed seasonal variations from May to October, the highest concentration of each congener appearing in June. The seasonal variation was more marked for OH-PBDEs than in MeO-PBDEs, but all congeners showed the same trends, except 6-MeO-BDE47 and 2′-MeO-BDE68, which did not significantly decline in concentrations after June. Biotic or abiotic debromination is suggested as a possible reason for the rapid decrease in methoxylated penta- and hexa-BDE concentrations observed in blue mussels from June to August, while the tetraBDE concentrations were stable. In addition, 1,3,7/1,3,8-tribrominated dibenzo-p-dioxins showed the same seasonal variation. The seasonal variations indicates natural formation and are unlikely to be due to transformation of anthropogenic precursors. The levels of PBDEs were fairly constant over time and considerably lower than those of the OH-PBDEs and MeO-PBDEs. The timing of the peaks in concentrations suggests that filamentous macro-algae may be important sources of these compounds found in the blue mussels from this Baltic Sea location.     

Long-term development of inorganic nutrients and chlorophyll alpha in the open northern Baltic Sea

Eutrophication is an ongoing process in most parts of the Baltic Sea. This article reports on the changes during recent decades of several eutrophication-related variables in the open sea areas surrounding Finland (wintertime nutrient concentrations, wintertime nutrient ratios, and summer time chlorophyll alpha concentrations at the surface). The sum of nitrate- and nitrite-nitrogen ([NO3+NO2]-N) was observed to increase nearly fourfold in the Northern Baltic Proper and the Gulf of Finland and almost double in the Bothnian Sea from the 1960s until the 1980s or 1990s. The increase was followed by a decrease, which was modest in the two former subregions. Phosphate-phosphorus (PO4-P) concentrations followed a similar pattern in the Northern Baltic Proper (threefold increase and subsequent slight decrease) and Bothnian Sea (30% increase and subsequent decrease), but increased throughout the study in the Gulf of Finland, with the present concentration being threefold to the measurements made in the early 1970s. The PO4-P concentration decreased throughout the study in the Bothnian Bay. Silicate-silicon (SiO4-Si) concentrations decreased 30-50% from the early 1970s to the late 1990s and increased 20-40% thereafter in the Northern Baltic Proper, the Gulf of Finland, and the Bothnian Sea. Chlorophyll alpha showed an increase of over 150% in the Northern Baltic Proper and the Gulf of Finland from the 1970s until the early 2000s. In the Bothnian Sea the chlorophyll alpha concentration increased more than 180% from the late 1970s until the late 1990s, and decreased thereafter. According to these long-term observations, the Gulf of Finland and Northern Baltic Proper show clear signs of eutrophication, which may be emphasized by hydrographical changes affecting the phytoplankton communities and thus the algal biomass.     

Metal concentrations in seabirds of the New Zealand region

Concentrations of the heavy metals cadmium, copper, lead, zinc, mercury and, in some individuals, methyl mercury were determined in a range of tissues of 64 tropical, subtropical, subantarctic and antarctic seabird taxa mostly from the New Zealand region. Although apparently natural, levels of cadmium and mercury in some species greatly exceed those known to have toxic effects in some terrestrial birds. Copper and zinc levels exhibited less inter-species variation than the non-essential metals cadmium and mercury. Cadmium concentrations were highest in kidney tissues but uniformly low in feathers. Total mercury concentrations showed most inter-species variation. Mean methyl mercury levels in liver tissues of several large procellariiforms represented less than 5% of the corresponding mean total mercury level. Lead concentrations were generally low or below the limits of detection, but elevated levels were measured in some coastal or scavenging species. In a significant number of species, mean concentrations of liver cadmium and mercury and kidney cadmium were greater in adults than in young birds. The reverse was true for copper. Mean zinc levels in liver did not differ between adults and young. High levels of cadmium in some species seem likely to be due to diet, whereas high levels of mercury probably reflect more closely the moult intervals which constrain the ability of birds to eliminate methyl mercury.     

Chemical characterization of fine aerosols in respect to water-soluble ions at the eastern Middle Adriatic coast

Fine particulate matter (PM2.5) concentrations at the Middle Adriatic coastal site of Croatia were affected by different air-mass inflows and/or local sources and meteorological conditions, and peaked in summer. More polluted continental air-mass inflows mostly affected the area in the winter period, while southern marine pathways had higher impact in spring and summer. Chemical characterization of the water-soluble inorganic and organic ionic constituents is discussed with respect to seasonal trends, possible sources, and air-mass inputs. The largest contributors to the PM2.5 mass were sea salts modified by the presence of secondary sulfate-rich aerosols indicated also by principal component analysis. SO42− was the prevailing anion, while the anthropogenic SO42− (anth-nssSO42−) dominantly constituted the major non-sea-salt SO42− (nssSO42−) fraction. Being influenced by the marine origin, its biogenic fraction (bio-nssSO42−) increased particularly in the spring. During the investigated period, aerosols were generally acidic. High Cl− deficit was observed at Middle Adriatic location for which the acid displacement is primarily responsible. With nssSO42− being dominant in Cl− depletion, sulfur-containing species from anthropogenic pollution emissions may have profound impact on atmospheric composition through altering chlorine chemistry in this region. However, when accounting for the neutralization of H2SO4 by NH3, the potential of HNO3 and organic acids to considerably influence Cl− depletion is shown to increase. Intensive open-fire events substantially increased the PM2.5 concentrations and changed the water-soluble ion composition and aerosol acidity in summer of 2015. To our knowledge, this work presents the first time-resolved data evaluating the seasonal composition of water-soluble ions and their possible sources in PM2.5 at the Middle Adriatic area. This study contributes towards a better understanding of atmospheric composition in the coastal Adriatic area and serves as a basis for the comparison with future studies related to the air quality at the coastal Adriatic and/or Mediterranean regions.     

Seasonal variability of oxidative biomarkers, lysosomal parameters, metallothioneins and peroxisomal enzymes in the Mediterranean mussel Mytilus galloprovincialis from Adriatic Sea

The Mediterranean mussel, Mytilus galloprovincialis, is a classical sentinel organism for monitoring the biological effects of contaminants through the use of molecular and cellular biomarkers. These biological responses can be modulated also by seasonal changes of both environmental and biological factors, potentially influencing responsiveness and sensitivity to pollutants. The aim of this study was to characterize in a reference mussel population from the Adriatic Sea, the natural fluctuations of several oxidative stress biomarkers widely used in ecotoxicological applications. Analyses of individual antioxidant defenses (catalase, glutathione S-transferases, glutathione reductase, glutathione peroxidases, levels of glutathione) were integrated with those of the total oxyradical scavenging capacity (TOSC-assay), which quantify the overall capability of a tissue to neutralize different forms of oxyradicals. Due to the close relationship between antioxidant efficiency and onset of various cellular alteration, the seasonal characterization was carried out also on lysosomal membrane stability, accumulation of malondialdehyde, neutral lipids and lipofuscin, levels of metallothioneins and activity of peroxisomal enzymes (acyl-CoA oxidase and d-aminoacid oxidase). Results indicated a significant seasonality for several biological responses; major variations occurred especially in spring and summer months suggesting the influence of natural factors, such as temperature, reproductive cycle and food availability. The observed seasonal oscillations revealed both similarities and differences with those reported for other Mediterranean mussel populations suggesting that opposite trends can occur when the same environmental prooxidant factors have a different regional influence.     

Metal accumulation in tissues of seabirds from Chaun, northeast Siberia, Russia

Concentrations of four essential elements (Fe, Mn, Zn, and Cu) and two toxic metals (Cd and Hg) were determined in selected tissues of 11 seabird species collected in Chaun, northeast Siberia. In oldsquaw, arctic tern and herring gull, zinc concentrations were correlated with Cd concentrations. Cadmium concentrations in all the species were highest in kidney and Hg in liver. Cd levels in the liver and kidney of herring gulls were higher than those observed from other breeding areas. Similarly, Hg concentrations were also high in the liver of herring gull. High concentrations of Cd and Hg found in some birds from Chaun might have arisen from exposure on migration.     

Biologic impact on the coastal belt of the province of Venice (Italy,Northern Adriatic Sea): preliminary analysis for the characterization of the bathing water profile

Background, aim and scope  

This paper presents a preliminary study of the water profile with reference to microbiological parameters, required by Directive 2006/07/EC (European Community 2006) concerning the management of bathing water quality, in the coastal belt of the Province of Venice (Italy, Northern Adriatic Sea). A historical database has been implemented with monitoring data for the period 2000–2006 (data on rivers, bathing and marine coastal waters and on the characterization of Wastewater Treatment Plant (WWTP) discharges) from the institutional activity of Veneto Regional Environmental Prevention and Protection Agency (ARPAV). An integrated areal analysis for the microbiological investigation of homogeneous stretches along the coast of the Province of Venice was performed for a preliminary characterization of the bathing water profile considering water quality status and existing pressure sources.     

Spatial and seasonal variations of polycyclic aromatic hydrocarbons in Haihe Plain, China

A dynamic fugacity model was developed to simulate the spatial and seasonal variations of PAHs in Haihe Plain, China. The calculated and measured concentrations exhibited good consistency in magnitude with deviations within a factor of 4 in air and 2 in soil. The spatial distributions of PAHs in air were mainly controlled by emission while the seasonal variations were dominated by emission and gas-particle partition. In soil, the spatial distributions of PAHs were controlled by the soil organic carbon content while the seasonal variations were insignificant. The severest soil contamination was observed in Shanxi and followed by the southwest of Hebei province. Transfer fluxes of total PAHs between air and soil were calculated. The spatial distribution of air-to-soil flux was closely related to the landcover while the soil-to-air flux changed with soil organic matter content. Monte Carlo simulation was done to evaluate the uncertainty of the estimated results in air.     

Dissolved heavy metal concentrations of the Kralkızı, Dicle and Batman dam reservoirs in the Tigris River basin,Turkey

Water samples were collected at monthly intervals during 1 year of monitoring from Kralk?z?, Dicle and Batman dam reservoirs in the Tigris River basin to assess the concentrations of dissolved heavy metals and to determine their spatial and seasonal variations. The results indicated that dissolved heavy metal concentrations in the reservoirs were very low, reflecting the natural background levels. The lowest total metal concentrations in the three dam reservoirs were detected at sampling sites close to the dam wall. However, the highest total concentrations were observed at sites, which are located at the entrance of the streams to the reservoirs. Fe, Cr and Ni were the most abundant elements in the reservoirs, whereas Cd and As were the less abundant. The mean concentrations of dissolved metals in the dam reservoirs never exceeded the maximum permitted concentrations established by EC (European Community), WHO and USEPA drinking water quality guidelines. All heavy metals showed significant seasonal variations. As, Cd, Cr, Cu, Fe, Ni and Pb displayed higher values in the dry season, while higher values for Zn in the wet season. Cluster analysis grouped all ten sampling sites into three clusters. Clusters 1 and 2, and cluster 3 corresponded to relatively low polluted and moderate polluted regions, respectively. PCA/FA demonstrated the dissolved metals in the dam reservoirs controlled by natural sources.     

Detection and quantitative analysis of organochlorine compounds (PCBs and DDTs) in deep sea fish liver from Mediterranean Sea

Background, aim and scope  

Polychlorinated biphenyls (PCB) and dichlorodiphenyltrichloroethane (DDT) concentrations were determined in the liver of two deep sea fish species, Mediterranean slimehead and blackfin sorcerer, from the Adriatic Sea (southeastern Mediterranean Sea).     

Concentrations and composition of organochlorine contaminants in different species of cephalopod molluscs from the Italian waters (Adriatic Sea)

Persistent organochlorines, such as polychlorinated biphenyls including coplanar congeners and DDT compounds were measured in the liver of different species of mollusc cephalopods: broadtail squid (Illex coindetii), horned octopus (Eledone moschata) and spider octopus (Octopus salutii) collected in two different areas of the Adriatic Sea (central and southern Adriatic Sea). The concentration of PCBs exceeded DDT ones in horned octopus (PCBs: 617.0 ngg(-1) lipid weight, DDTs: 188.0 ngg(-1) lipid weight) and in spider octopus (PCBs: 590.0 ngg(-1) lipid weight, DDTs: 293.0 ngg(-1) lipid weight), while in broadtail squid PCB load (748.0 ngg(-1) lipid weight) was similar to those of DDTs (514.5 ngg(-1) lipid weight). No significant difference in PCB levels was observed among species, while DDT concentrations were higher in broadtail squid than in horned octopus and spider octopus. DDTs composition showed slight differences in relation to species, thought p,p'-DDE was the predominant compound in all cephalopod species (broadtail squid: 88.1%, horned octopus 94.1%, spider octopus: 97.5%). PCB isomer profiles were similar among species being hexachlorinated isomers the most abundant, followed by penta- and heptachlorobiphenyls, while tri- and tetrachlorobiphenyls made up a small percentage of the total PCB residues. Regarding coplanar congeners, non-ortho PCBs were below the detection limit in all samples and the 2,3,7,8-TCDD toxic equivalent (TEQ) concentrations were very low. The influence of biological and ecological factors (size/weight and location) on the bioaccumulation of organochlorine compounds has been discussed.     

Trace element (Cd, Cu, Hg, Se, Zn) accumulation and tissue distribution in loggerhead turtles (Caretta caretta) from the Western Mediterranean Sea (southern Italy)

Cadmium (Cd), copper (Cu), mercury (Hg), selenium (Se) and zinc (Zn) were determined in the liver, kidney and muscle of 29 loggerhead turtles, Caretta caretta, from the South Tyrrhenian Sea (Western Mediterranean). No significant differences (p>0.05) were detected between males and females. Trace element concentrations were not influenced by the size of the specimen except Se in the liver, which was negatively correlated with the curved carapace length (p<0.001). Muscles generally displayed the lowest trace element burdens, with the exception of Zn which contained concentrations as high as 176 microgg-1dwt. Kidneys displayed the highest Cd and Se mean concentrations (57.2+/-34.6 and 15.5+/-9.1 microgg-1dwt, respectively), while liver exhibited the highest Cu and Hg levels (37.3+/-8.7 and 1.1+/-1.7 microgg-1dwt, respectively). Whichever tissue is considered, the toxic elements had elevated coefficients of variation (i.e. from 60% to 177%) compared to those of the essential ones (i.e. from 14% to 65%), which is a consequence of homeostatic processes for Cu, Se and Zn. Globally, the concentrations of Hg remained low in all the considered tissues, possibly the result of low trophic level in sea turtles. In contrast, the diet of loggerhead turtles would result in a significant exposure to Cd. Highly significant correlations between Cd and Cu and Zn in the liver and kidney suggest that efficient detoxification processes involving MT occur which prevent Cd toxicity in loggerhead turtles.     

Persistence of polycyclic aromatic hydrocarbons in sediments in the deeper area of the Northern Adriatic Sea (Mediterranean Sea)

The Po Valley is the most important agricultural and industrial area of Adriatic basin. In this area there are several rivers which transport polycyclic aromatic hydrocarbons (PAHs) into the sea via suspended particulate matter. This study describes the persistence of PAHs in the deep and coastal sediments of the Northern Adriatic. Different environmental conditions were studied: salinity, temperature, sunlight, sediment particle size and organic matter in sediment. The average conditions in the deep areas of the Northern Adriatic are: salinity higher than 37, temperature lower than 11 °C, darkness and clayey sediments with a high organic matter content. These conditions increase the persistence of the PAHs in the deep area of the Northern Adriatic.     

The effects of cadmium and zinc interactions on the accumulation and tissue distribution of zinc and cadmium in lettuce and spinach

The interactions between Zn and Cd on the concentration and tissue distribution of these metals in lettuce and spinach were studied at levels corresponding to background and Zn-Cd contaminated sites. Plants were grown in nutrient solutions containing 0.398-8.91 microM Zn and 0.010-0.316 microM Cd. Cadmium accumulated more in old than in young leaves of both crops at any solution Cd level, whereas Zn followed that pattern only at Zn levels > or = 3.16 microM. Increasing solution Cd increased Zn concentrations in young leaves of lettuce but not of spinach, regardless of Zn levels. Cadmium concentrations in young leaves of both crops decreased exponentially with increasing solution Zn at low (0.0316 microM) but not at high (0.316 microM) solution Cd. The Zn: Cd concentration ratios in young leaves of lettuce and spinach grown at 0.316 microM Cd became greater as the solution Zn increased. Cadmium and Zn concentrations in young leaves were related more closely to the relative concentrations of Zn and Cd in solution than were the concentrations in old leaves, especially in lettuce. Studies of Zn-Cd interactions and Cd bioavailability should differentiate between basal and upper leaves of lettuce and spinach. Compared to Cd-only pollution, Zn-Cd combined pollution may not decrease Cd concentrations in lettuce and spinach edible tissues, but because it increases their Zn concentrations it lowers plant Cd bioavailability.