In situ accumulation of copper, chromium, nickel, and zinc in soils used for long-term waste water reclamation.

We studied the long-term in situ accumulation of Cu, Cr, Ni, and Zn in the soil profile of a large-scale effluent recharge basin after 24 yr of operation in a wastewater reclamation plant using the Soil Aquifer System approach in the Coastal Plain of Israel. The objective was to quantify metals accumulation in the basin's soil profile, clarify retention mechanisms, and calculate material balances and metal removal efficiency as the metal loads increase. Effluent recharge led to measurable accumulation, relative to the pristine soil, of Ni and Zn in the 0- to 4-m soil profile, with concentration increases of 0.3 to 1.3 mg kg(-1) and 2.9 to 6.4 mg kg(-1), respectively. Copper accumulated only in the 0- to 1-m top soil layer, with concentration increase of 0.28 to 0.76 mg kg(-1). Chromium concentration increased by 3.1 to 7.3 mg kg(-1) in the 0- to 1-m horizon and 0.9 to 2.3 mg kg(-1) at deeper horizons. Sequential selective extraction showed Cu tended to be preferentially retained by Fe oxides and organic matter (OM), Cr by OM, Ni by OM, and carbonate and Zn by carbonate. The average total retained amounts of Cu, Cr, Ni, and Zn were 0.7 +/- 1.0, 13.6 +/- 4.8, 4.3 +/- 3.6, and 28.7 +/- 5.4 g per a representative unit soil slab (1 m(2) x 4 m) of the basin, respectively. This amounts to 3.6 +/- 4.9%, 79.5 +/- 28.0%, 8.0 +/- 6.9%, and 9.3 +/- 1.8% of the Cu, Cr, Ni, and Zn loads, respectively, applied during 24 yr of effluent recharge (total of approximately 1880 m effluent load). The low long-term overall removal efficiency of the metals from the recharged effluent in the top horizon may be due to the metals' low concentrations in the recharged effluent and the low adsorption affinity and retention capacity of the sandy soil toward them. This leads to attainment of a quasi-equilibrium and a steady state in element distribution between the recharged effluent solution and the soil after few years of recharge and relatively small cumulative effluent loadings.

Phosphorous retardation and breakthrough into well water in a soil-aquifer treatment (SAT) system used for large-scale wastewater reclamation.

Retardation and breakthrough of phosphorous in the soil/sediment profiles of a SAT system at the Shafdan wastewater treatment plant, Israel, were investigated in situ. Area-weighted average effluent load to the whole site was 65 m yr(-1). Annual average concentrations of P in the recharged effluent ranged between about 1.5 and 7.7 mg L(-1) during 25 yr of operation, while P in groundwater remained 40 m sandy soil/sediment formations. By combining results of isotherm tests, long-term monitoring of phosphorous (P) in solid and liquid phases of the recharge site, a simple multi-cell tracer-movement model and measured chloride breakthrough curves to the groundwater we calculated P distribution coefficients and estimated the retardation factor of P. Laboratory measured, isotherm-based distribution coefficient, Kd(I), was about 4-6 L kg(-1) at equilibrium P concentration <6 mg L(-1), while field-based Kd(F) was considerably higher, reaching about 20-55 L kg(-1) after a load of around 1800 m effluent was recharged. Measured P breakthrough times into two shallow observation wells were 19-21 yr. Calculated P breakthrough times using Kd(F) data agreed with observations while those calculated using Kd(I) grossly underestimated retardation and predicted much shorter breakthrough times. This validated the approach and model used. Estimated P breakthrough times to the deeper observation wells and the recovery wells are more than 100 yr and 400-1100 yr, respectively. These estimates show that P contamination of the reclaimed effluents in the Shafdan plant will not be a problem in the foreseeable future.

Novel approach for quantitatively estimating element retention and material balances in soil profiles of recharge basins used for wastewater reclamation.

We investigated changes in element content and distribution in soil profiles in a study designed to monitor the geochemical changes accruing in soil due to long-term secondary effluent recharge, and its impact on the sustainability of the Soil Aquifer Treatment (SAT) system. Since the initial elemental contents of the soils at the studied site were not available, we reconstructed them using scandium (Sc) as a conservative tracer. By using this approach, we were able to produce a mass-balance for 18 elements and evaluate the geochemical changes resulting from 19 years of effluent recharge. This approach also provides a better understanding of the role of soils as an adsorption filter for the heavy metals contained in the effluent. The soil mass balance suggests 19 years of effluent recharge cause for a significant enrichment in Cu, Cr, Ni, Zn, Mg, K, Na, S and P contents in the upper 4m of the soil profile. Combining the elements lode record during the 19 years suggest that Cr, Ni, and P inputs may not reach the groundwater (20 m deep), whereas the other elements may. Conversely, we found that 58, 60, and 30% of the initial content of Mn, Ca and Co respectively leached from the upper 2-m of the soil profile. These high percentages of Mn and Ca depletion from the basin soils may reduce the soil's ability to buffer decreases in redox potential pe and pH, respectively, which could initiate a reduction in the soil's holding capacity for heavy metals.

Heavy metal retention and partitioning in a large-scale soil-aquifer treatment (SAT) system used for wastewater reclamation.

Soil aquifer treatment (SAT) of wastewater relies on extensive biogeochemical processes in the soil and aquifer to achieve large-scale and economic reclamation of municipal effluents. Removal of trace metals from the wastewater is a prime objective in the operation, but the long-term sustainability of the adsorptive filtration capacity of the soils is an open question. Solid/solution partitioning (measured by the distribution coefficient, K(d)) and solid/solid partitioning (measured by selective sequential dissolution, SSD) of heavy metals were measured in soils sampled from active recharge basins in a wastewater reclamation plant and were compared to the adjacent pristine dune. K(d) values for the adsorption of Cu, Ni and Zn, measured in short-term adsorption experiments positively and significantly correlated with solution pH. Quantitative estimation of Cu, Ni and Zn adsorption on multi-sorbents indicated that surface adsorption and precipitation on Fe oxides and/or carbonate may be the major mechanisms of metal retention in these soils. SSD analyses of metal partitioning in soils exposed to approximately 20yr of effluent recharge showed that all solid-phase components, including the most stable 'residual' component, competed for and retained added Cu and Zn. Copper preferentially partitioned into the oxide component (32.0% of the soil-accumulated metal) while Zn preferentially partitioned into the carbonate component (51.6% of the soil-accumulated metal).

Pathways and kinetics of redistribution of cobalt among solid-phase fractions in arid-zone soils under saturated regime.

An adequate supply of Co in pasture is important to the health of grazing animals. Bio-availability of Co in soils is largely depended upon its distribution among solid-phase fractions. Distribution of cobalt in six arid-zone soils and its redistribution among the solid-phase fractions during long-term saturated paste incubation were studied. Cobalt was fractionated by a selective sequential dissolution procedure into six empirically defined fractions. Concentrations of total Co and Mn or Fe, and Co and Mn fractionation pattern were strongly correlated in the soils. During saturated incubation, Co in soils was redistributed mainly from the Mn oxide bound, and to some extent, Fe oxide bound and organic matter bound fractions into the carbonate bound fraction. During saturated incubation, significant correlations were found between concentrations of Co and Mn in the Mn oxide bound, Fe oxide bound and carbonate bound fractions. Also, significant correlations between concentrations of Co and Fe in the Fe oxide bound fraction were present. However, a negative correlation between concentrations of Co and Fe in the Mn oxide bound fraction was observed. The rates of redistribution of Co between these solid-phase components were initially high: major changes occurred in the first 3 days in the sandy soil and the first 18 days in the loessial soil. Afterwards, the rates of change slowed but changes in redistribution continued during the rest of the study period of one year.

Assessment of global industrial-age anthropogenic arsenic contamination.

Arsenic, a carcinogenic trace element, threatens not only the health of millions of humans and other living organisms, but also global sustainability. We present here, for the first time, the global industrial-age cumulative anthropogenic arsenic production and its potential accumulation and risks in the environment. In 2000, the world cumulative industrial-age anthropogenic arsenic production was 4.53 million tonnes. The world-wide coal and petroleum industries accounted for 46% of global annual gross arsenic production, and their overall contribution to industrial-age gross arsenic production was 27% in 2000. Global industrial-age anthropogenic As sources (as As cumulative production) follow the order: As mining production>As generated from coal>As generated from petroleum. The potential industrial-age anthropogenic arsenic input in world arable surface in 2000 was 2.18 mg arsenic kg(-1), which is 1.2 times that in the lithosphere. The development of substitute materials for arsenic applications in the agricultural and forestry industries and controls of arsenic emissions from the coal industry may be possible strategies to significantly decrease arsenic pollution sources and dissipation rates into the environment.

Industrial age anthropogenic inputs of heavy metals into the pedosphere.

Heavy metals have been increasingly released into our environment. We present here, for the first time, the global industrial age production of Cd, Cu, Cr, Hg, Ni, Pb, and Zn, and their potential accumulation and environmental effects in the pedosphere. World soils have been seriously polluted by Pb and Cd and slightly by Zn. The potential industrial age anthropogenic Pb, Hg, and Cd inputs in the pedosphere are 9.6, 6.1, and 5.2 times those in the lithosphere, respectively. The potential anthropogenic heavy metal inputs in the pedosphere increased tremendously after the 1950s, especially for Cr and Ni. In 2000, the cumulative industrial age anthropogenic global production of Cd, Cr, Cu, Hg, Ni, Pb, and Zn was 1.1, 105, 451, 0.64, 36, 235, and 354 million tonnes, respectively. The global industrial age metal burdens per capita (in 2000) were 0.18, 17.3, 74.2, 0.10, 5.9, 38.6, and 58.2 kg for Cd, Cr, Cu, Hg, Ni, Pb, and Zn, respectively. Acidification may increase the bioavailability and toxicity of heavy metals in the pedosphere. The improvement of industrial processing technology reducing the metal dispersion rate, the recycling of metal-containing outdated products, by-products and wastes, and the development of new substitute materials for heavy metals are possible strategies to minimize the effects of heavy metals on our environment.