Turbid Waters and Clearer Standards: Refining Water Quality Criteria for Coastal Environments by Encompassing Metal Bioavailability from Suspended Particles.

Suspended particulate matter (SPM) carries a major fraction of metals in turbid coastal waters, markedly influencing metal bioaccumulation and posing risks to marine life. However, its effects are often overlooked in current water quality criteria for metals, primarily due to challenges in quantifying SPM's contribution. This contribution depends on the SPM concentration, metal distribution coefficients (Kd), and the bioavailability of SPM-bound metals (assimilation efficiency, AE), which can collectively be integrated as a modifying factor (MF). Accordingly, we developed a new stable isotope method to measure metal AE by individual organisms from SPM, employing the widely distributed filter-feeding clam Ruditapes philippinarum as a representative species. Assessing SPM from 23 coastal sites in China, we found average AEs of 42% for Zn, 26% for Cd, 20% for Cu, 8% for Ni, and 6% for Pb. Moreover, using stable isotope methods, we determined metal Kd of SPM from these sites, which can be well predicted by the total organic carbon and iron content (R2 = 0.977). We calculated MFs using a Monte Carlo method. The calculated MFs are in the range 9.9-43 for Pb, 8.5-37 for Zn, 2.9-9.7 for Cu, 1.4-2.7 for Ni, and 1.1-1.6 for Cd, suggesting that dissolved-metal-based criteria values should be divided by MFs to provide adequate protection to aquatic life. This study provides foundational guidelines to refine water quality criteria in turbid waters and protect coastal ecosystems.

Properties influencing flux and diatom uptake of mercury and methylmercury from estuarine sediments.

Mercury (Hg) is a conspicuous and persistent global pollutant. Ionic Hg can be methylated into noxious methylmercury (CH3Hg), which biomagnifies in marine tropic webs and poses a health risk to humans and organisms. Sediment Hg methylation rates are variable, and the output flux of created CH3Hg are dependent on sediment characteristics and environmental factors. Thus, uncertainties remain about the formation and flux of CH3Hg from sediment, and how this could contribute to the bioaccumulative burden for coastal organisms in shallow ecosystems. Cores were collected from 3 estuarine locations along the Eastern USA to examine how sediments characteristics influence the introduction of Hg and CH3Hg into the base of the food chain. Stable isotopes of inorganic 200Hg and CH3199Hg were injected into sediments of individual cores, with cultured diatoms constrained to overlying waters. Five different treatments were done on duplicate cores, spiked with: (1) no Hg isotopes (control); (2) inorganic 200Hg; (3) CH3199Hg; (4) both 200Hg and CH3199Hg isotopes, (5) both 200Hg and CH3199Hg into overlying waters (not sediment). Experimental cores were incubated for 3 days under temperature and light controlled conditions. These results demonstrate that upper sediments characteristics lead to high variability in Hg cycling. Notably, sediments which contained abundant and peaty organic material (∼28 %LOI), had the highest pore water DOC (3206 µM) and displayed bands of sulfur reducing bacteria yielded the greatest methylation rate (1.97 % day-1) and subsequent diatom uptake of CH3200Hg (cell quota 0.18 amol/cell) in the overlying water.

World war munitions as a source of mercury in the southwest Baltic Sea.

Mercury (Hg) fulminate was used as a primary fuse in World War (WW) munitions, and may consequently be a Hg source for impacted environments. Mercury is a conspicuous and persistent pollutant, with methylmercury (MeHg) acting as a notorious neurotoxin. Considerable amounts of munitions were intentionally dumped in the North Sea and Baltic Sea following the First and Second WWs. After more than 70 years on the seafloor many munitions have corroded and likely release explosive compounds, including Hg fulminate. The Germany coastal city of Kiel was a manufacturing centre for submarines, and accordingly a prominent target for bombing and post-war disarmament. We collected water and sediment samples around Kiel Bay to assess regional levels and quantify any Hg contamination. The munition dump site Kolberger Heide (KH) and a former anti-aircraft training center Dänisch-Nienhof are situated in Kiel Bay, and were targeted for sampling. Sediment Hg concentrations around KH were notably elevated. Average Hg concentrations in KH sediments were 125 ± 76 ng/g, compared to 14 ± 18 ng/g at background (control) sites. In contrast, dissolved Hg in the water column exhibited no site variations, all ranging between 0.8 and 2.1 pM. Methylmercury in sediments and waters did not have enhanced concentrations amongst sites (<30 pg/g and <50 fM, respectively). Sediment-water exchange experiments showed elevated Hg and MeHg fluxes (i.e. >400 pmol m-2 d-1 MeHg) at one KH location, however remaining cores had low to no Hg and MeHg output (<0-27 pmol m-2 d-1 MeHg). Thus, sediments in Kiel Bay proximate to WW munitions could harbor and form a source of Hg, however water column mixing and removal processes attenuate any discharge from the seafloor to overlying waters.

Effects of salinity and temperature on seawater dissolution rate of initial detonation agent mercury fulminate.

Mercury fulminate (HgFu) was used as an initial detonator for World War I and II munitions. Its presence in previously discarded and dumped munitions could potentially supply mercury pollution into coastal ecosystems where bygone weaponries reside. There is evidence that historical munitions have already contributed mercury pollution in coastal environments, and millions remain embedded in sediments and subjected to further weakening via corrosion under environmental conditions. Experiments were undertaken assessing HgFu dissolution under varying temperature and salinity conditions to constrain controls on mercury release into marine environments. Our results show that HgFu discharge is strongly temperature dependent, with dissolution rate constants increasing from ∼0.4 mg cm-2 d-1 at 5 °C to ∼2.7 mg cm-2 d-1 at 30 °C. No significant differences were observed between freshwater and seawaters up to 36 psu, except at 5 °C. These experiments provide a basis for modeling HgFu release from underwater munitions and its dynamics in coastal environments.

Mercury and methylmercury uptake and trophic transfer from marine diatoms to copepods and field collected zooplankton.

Mercury (Hg) and methylmercury (CH3Hg) are found at trace levels in most marine waters. These species, particularly CH3Hg, then ominously bioaccumulate through marine food chains eventually reaching potentially harmful levels in top oceanic wildlife. Accordingly, it is important to measure and evaluate uptake at environmentally relevant concentrations where trophic transfer initiates; during uptake in primary producers, and consumption by plankton grazers. Experiments using cultured copepods (Acartia tonsa) and field zooplankton assemblages were performed with two different sized diatom species labeled with stable isotopes of inorganic Hg (200Hg) and CH3Hg (CH3199Hg) at different concentrations. We observed size-specific effects on algal uptake and transfer to copepods, in addition to effects of Hg species concentration. Prey size effects were likewise observed on copepod assimilation efficiencies (AE). Average AE of 200Hg for copepods feeding on smaller diatoms was 50%, and 39% for larger diatoms. The AEs were much greater for CH3199Hg, yielding 71% for the smaller and 88% for the larger diatoms. These experiments add evidence demonstrating a significant relationship between Hg and CH3Hg exposure concentration and subsequent algal uptake and transfer to zooplankton. Furthermore, results imply that facilitated uptake of CH3Hg into algae occurs at low (~pM) concentrations, which has been suggested but not confirmed in previous research.

Freshwater discharges drive high levels of methylmercury in Arctic marine biota.

Elevated levels of neurotoxic methylmercury in Arctic food-webs pose health risks for indigenous populations that consume large quantities of marine mammals and fish. Estuaries provide critical hunting and fishing territory for these populations, and, until recently, benthic sediment was thought to be the main methylmercury source for coastal fish. New hydroelectric developments are being proposed in many northern ecosystems, and the ecological impacts of this industry relative to accelerating climate changes are poorly characterized. Here we evaluate the competing impacts of climate-driven changes in northern ecosystems and reservoir flooding on methylmercury production and bioaccumulation through a case study of a stratified sub-Arctic estuarine fjord in Labrador, Canada. Methylmercury bioaccumulation in zooplankton is higher than in midlatitude ecosystems. Direct measurements and modeling show that currently the largest methylmercury source is production in oxic surface seawater. Water-column methylation is highest in stratified surface waters near the river mouth because of the stimulating effects of terrestrial organic matter on methylating microbes. We attribute enhanced biomagnification in plankton to a thin layer of marine snow widely observed in stratified systems that concentrates microbial methylation and multiple trophic levels of zooplankton in a vertically restricted zone. Large freshwater inputs and the extensive Arctic Ocean continental shelf mean these processes are likely widespread and will be enhanced by future increases in water-column stratification, exacerbating high biological methylmercury concentrations. Soil flooding experiments indicate that near-term changes expected from reservoir creation will increase methylmercury inputs to the estuary by 25-200%, overwhelming climate-driven changes over the next decade.