Legacy groundwater pollution as a source of mercury enrichment in marine food web, Haifa Bay, Israel.

Haifa Bay (HB), located along the northern Mediterranean shore of Israel was polluted with Hg from a chlor-alkali plant (ECI) and from the Qishon River industries, for decades. From the mid-1980s industrial Hg loads into HB decreased dramatically until their complete cessation in 2000. Consequently, concentrations in marine biota and sediments decreased almost to reference levels. However, during 2006-2014, an unexpected increase of total Hg (THg) concentrations was observed in three commercial fish species collected at northern HB (N.HB). To determine the cause of this increase, THg and methyl Hg (MeHg) were measured in seawater, coastal groundwater, suspended particulate matter, plankton, macroalgae, benthic fauna, and in marine and beach sediments. THg in groundwater and sediments from the vicinity of ECI were extremely high (up to 251 µg L-1 and 2200 ng g-1, respectively). MeHg concentrations in groundwater were low and constituted <0.1% of THg, except in the surf zone opposite the ECI, where MeHg constituted 0.2% of the THg. THg and MeHg concentrations were consistently higher in benthic biota and plankton from N.HB and northwards, compared to corresponding samples from southern HB (S.HB) and the reference site (RS). MeHg in bivalves and sponges from N.HB and SZ was higher than from S.HB and RS, despite having similar THg concentrations, which suggests a stronger source of MeHg in N.HB. Our findings suggest that the discharge into N.HB of Hg polluted groundwater under the ECI increased during the period 2006-2014. The Hg was assimilated by plankton or adsorbed onto inorganic particles, which were further ingested by benthic and pelagic consumers, as well as transported northward with the alongshore current. These findings demonstrate for the first time the potential of relic pollution in groundwater to increase heavy metal burdens in local marine food webs.

Twenty two years of sewage sludge marine disposal monitoring in the Eastern Mediterranean Sea: Impact on sediment quality and infauna and the response to load reduction.

Effects of sewage sludge disposal on sediments and infauna are presented in a unique long-term (22years) data set from the Eastern Mediterranean. While organic carbon (Corg) and metals affected sediment quality in an area which size varied seasonally, the infauna exhibited seasonal "boom and bust" cycle. Metal concentrations declined following load reduction. However, Corg did not decrease and infaunal abundance, closely related to Corg, varied with changes in environmental forcing. Mild winters affected the infaunal populations at the heavily impacted stations, due to anoxic conditions. Planned cessation of disposal is estimated to reduce Corg and metal concentrations to pre-discharge levels. Yet the resettling biota is expected to differ significantly from the pre-discharge one and consist in large part of Erythraean non indigenous species.

Mercury speciation in sediments at a municipal sewage sludge marine disposal site.

Mercury speciation was performed in excess activated sewage sludge (ASS) and in marine sediments collected at the AAS disposal site off the Mediterranean coast of Israel in order to characterize the spatial and vertical distribution of different mercury species and assess their environmental impact. Total Hg (HgT) concentrations ranged between 0.19 and 1003ng/g at the polluted stations and 5.7 and 72.8ng/g at the background station, while the average concentration in ASS was 1181+/-273ng/g. Only at the polluted stations did HgT concentrations decrease exponentially with sediment depth, reaching background values at 16-20cm, the vertical distribution resulting from mixing of natural sediment with ASS solids and bioturbation by large populations of polycheates. Average Methyl Hg (MeHg) concentration in ASS was 39.7+/-7.1ng/g, ca. 3% of the HgT concentration, while the background concentrations ranged between 0.1 and 0.61ng/g. MeHg concentrations in surficial polluted sediments were 0.7-5.9ng/g (ca. 0.5% of the HgT) and decreased vertically, similar to HgT. A positive correlation between MeHg and Hg only at the polluted stations, higher MeHg concentrations at the surface of the sediment and not below the redoxline, and no seasonality in the concentrations suggest that the MeHg originated from the ASS and not from in situ methylation. By doing selective extractions, we found that ca. 80% of the total Hg in ASS and polluted sediments was strongly bound to amorphous organo-sulfur and to inorganic sulfide species that are not bioavailable. The fractions with potential bioaccessible Hg had maximal concentrations in the range in which biotic effects should be expected. Therefore, although no bioaccumulation was found in the biota in the area, the concentration in the polluted sediments are not negligible and should be carefully monitored.

Nature of phosphorus limitation in the ultraoligotrophic eastern Mediterranean.

Phosphate addition to surface waters of the ultraoligotrophic, phosphorus-starved eastern Mediterranean in a Lagrangian experiment caused unexpected ecosystem responses. The system exhibited a decline in chlorophyll and an increase in bacterial production and copepod egg abundance. Although nitrogen and phosphorus colimitation hindered phytoplankton growth, phosphorous may have been transferred through the microbial food web to copepods via two, not mutually exclusive, pathways: (i) bypass of the phytoplankton compartment by phosphorus uptake in heterotrophic bacteria and (ii) tunnelling, whereby phosphate luxury consumption rapidly shifts the stoichiometric composition of copepod prey. Copepods may thus be coupled to lower trophic levels through interactions not usually considered.

Sewage sludge impact on sediment quality and benthic assemblages off the Mediterranean coast of Israel-a long-term study.

The distributions of benthic assemblages, heavy metals and organic carbon (Corg) in sediments were examined during a long-term study at a sewage sludge disposal site off the Mediterranean coast of Israel. The disposal of sewage sludge has a marked but localized, seasonally dependent, impact on the benthic assemblages and sediment quality. Elevated concentrations of Corg, Hg, Cd, Cu, Zn, Pb, and to a lesser degree Ni in the sediments were detected mostly northward of the sewage outfall, in the direction of the prevalent longshore current. High concentrations of Corg and metals were reflected by elevated populations of tolerant and opportunistic polychaetes in spring and by an azoic zone in fall. The impacted area extended mainly towards the north (up to ca. 4 km) and to a lesser extent south of the outfall (up to ca. 2.5 km). No evidence of increased accumulation of sewage sludge with time was found, nor of pollutants associated with it. Principal component analysis (PCA) grouped the anthropogenic metals and Corg with infaunal abundance for the spring surveys, while biotic diversity was negatively correlated with the pollutants. In the PCA of fall surveys, abundance was negatively correlated with the pollutants, decreasing with increased concentration of Corg and anthropogenic metals. We suggest that the seasonal pattern shown by infaunal abundance, anthropogenic metals and Corg is due to the stratification of the water column from spring to fall on one-hand and winter storms on the other. Winter storms resuspend and disperse the fine organic particles, sweeping the site clean of sludge; accumulation of sludge takes place throughout the quiescent periods of the year, when stratification is reestablished. The disposal site is dispersive and the spatial extent of the impacted area varies seasonally and interannually. This monitoring study, in addition to addressing specific questions about sewage sludge impact, represents an unusually large and unique set of long-term measurements that will serve as a basis to evaluate the site recovery following the cessation of disposal.