Arsenic behaviour from groundwater and soil to crops:impacts on agriculture and food safety

High levels of As in groundwater commonly found in Bangladesh and other parts of Asia not only pose a risk via drinking water consumption but also a risk in agricultural sustainability and food safety. This review attempts to provide an overview of current knowledge and gaps related to the assessment and management of these risks, including the behaviour of As in the soil-plant system, uptake, phytotoxicity, As speciation in foods, dietary habits, and human health risks. Special emphasis has been given to the situation in Bangladesh, where groundwater via shallow tube wells is the most important source of irrigation water in the dry season. Within the soil-plant system, there is a distinct difference in behaviour of As under flooded conditions, where arsenite (AsIII) predominates, and under nonflooded conditions, where arsenate (AsV) predominates. The former is regarded as most toxic to humans and plants. Limited data indicate that As-contaminated irrigation water can result in a slow buildup of As in the topsoil. In some cases the buildup is reflected by the As levels in crops, in others not. It is not yet possible to predict As uptake and toxicity in plants based on soil parameters. It is unknown under what conditions and in what time frame As is building up in the soil. Representative phytotoxicity data necessary to evaluate current and future soil concentrations are not yet available. Although there are no indications that crop production is currently inhibited by As, long-term risks are clearly present. Therefore, with concurrent assessments of the risks, management options to further prevent As accumulation in the topsoil should already have been explored. With regard to human health, data on As speciation in foods in combination with food consumption data are needed to assess dietary exposure, and these data should include spatial and seasonal variability. It is important to control confounding factors in assessing the risks. In a country where malnutrition is prevalent, levels of inorganic As in foods should be balanced against the nutritional value of the foods. Regarding agriculture, As is only one of the many factors that may pose a risk to the sustainability of crop production. Other risk factors such as nutrient depletion and loss of organic matter also must be taken into account to set priorities in terms of research, management, and overall strategy.

Increase in rice grain arsenic for regions of Bangladesh irrigating paddies with elevated arsenic in groundwaters.

Concern has been raised by Bangladeshi and international scientists about elevated levels of arsenic in Bengali food, particularly in rice grain. This is the first inclusive food market-basket survey from Bangladesh, which addresses the speciation and concentration of arsenic in rice, vegetables, pulses, and spices. Three hundred thirty aman and boro rice, 94 vegetables, and 50 pulse and spice samples were analyzed for total arsenic, using inductivity coupled plasma mass spectrometry (ICP-MS). The districts with the highest mean arsenic rice grain levels were all from southwestern Bangladesh:? Faridpur (boro) 0.51 > Satkhira (boro) 0.38 > Satkhira (aman) 0.36 > Chuadanga (boro) 0.32 > Meherpur (boro) 0.29 µg As g-1. The vast majority of food ingested arsenic in Bangladesh diets was found to be inorganic; with the predominant species detected in Bangladesh rice being arsenite (AsIII) or arsenate (AsV) with dimethyl arsinic acid (DMAV) being a minor component. Vegetables, pulses, and spices are less important to total arsenic intake than water and rice. Predicted inorganic arsenic intake from rice is modeled with the equivalent intake from drinking water for a typical Bangladesh diet. Daily consumption of rice with a total arsenic level of 0.08 µg As g-1 would be equivalent to a drinking water arsenic level of 10 µg L-1. Concern has been raised by Bangladeshi and international scientists about elevated levels of arsenic in Bengali food, particularly in rice grain. This is the first inclusive food market-basket survey from Bangladesh, which addresses the speciation and concentration of arsenic in rice, vegetables, pulses, and spices. Three hundred thirty aman and boro rice, 94 vegetables, and 50 pulse and spice samples were analyzed for total arsenic, using inductivity coupled plasma mass spectrometry (ICP-MS). The districts with the highest mean arsenic rice grain levels were all from southwestern Bangladesh:? Faridpur (boro) 0.51 > Satkhira (boro) 0.38 > Satkhira (aman) 0.36 > Chuadanga (boro) 0.32 > Meherpur (boro) 0.29 µg As g-1. The vast majority of food ingested arsenic in Bangladesh diets was found to be inorganic; with the predominant species detected in Bangladesh rice being arsenite (AsIII) or arsenate (AsV) with dimethyl arsinic acid (DMAV) being a minor component. Vegetables, pulses, and spices are less important to total arsenic intake than water and rice. Predicted inorganic arsenic intake from rice is modeled with the equivalent intake from drinking water for a typical Bangladesh diet. Daily consumption of rice with a total arsenic level of 0.08 µg As g-1 would be equivalent to a drinking water arsenic level of 10 µg L-1.

Lead isotopes and lead shot ingestion in the globally threatened marbled teal (Marmaronetta angustirostris) and white-headed duck (Oxyura leucocephala)

Lead isotope ratios ((206)Pb/(207)Pb and (208)Pb/(207)Pb) and concentrations in the livers and bones of marbled teal and white-headed duck found dead or moribund were determined in order to establish the main lead source in these waterfowl species. Lead concentrations in bone (dry weight) and liver (wet weight) were found to be very high in many of the white-headed ducks (bone: geometric mean=88.9 ppm, maximum=419 ppm; liver: geometric mean=16.8 ppm, maximum=57.0 ppm). Some of the marbled teal had high lead levels in the bones but liver lead levels were all low (bone: geometric mean=6.13 ppm, maximum=112 ppm; liver: geometric mean=0.581 ppm, maximum=4.77 ppm). Ingested lead shot were found in 71% of the white-headed duck and 20% of the marbled teal. The (206)Pb/(207)Pb ratio in livers and bones of white-headed ducks and marbled teals showed no significant differences compared to the ratios obtained from lead shot. The (206)Pb/(207)Pb ratio in bones of marbled teal ducklings with the highest lead concentrations tended to resemble the ratios of lead shot, which supports our hypothesis that the lead was derived from the hens. We also found that the lead ratios of lead shot and lead ratios described for soils in the area overlapped, but also that the isotopic ratio (206)Pb/(207)Pb in lead shot used in Spain has a narrow range compared with those used in North America. The principal source of lead in many of these birds was, however, most likely lead shot, as supported by the similar isotopic ratios, high lead concentrations in tissues and evidence of ingested shot.

Ecotoxicological screening of Kenyan tannery dust using a luminescent-based bacterial biosensor

Ecotoxicological screening of dust sampled throughout a Kenyan tannery was conducted using a luminescence (lux)-based bacterial biosensor for both solid and liquid assays. This was complemented by chemical analysis in an attempt to identify possible causative toxic components. The biosensor results showed a highly significant (p <0.001) difference in both solid and liquid phase toxicity in samples collected from various identified sampling points in the tannery. A positive correlation was observed between results of the solid and liquid phase techniques, for most of the sampling points indicating that the toxic contaminants were bioavailable both in the solid and liquid state. However, the results generally indicated toxicity associated with liquid phase except certain areas in solid phase such as chemical handling, buffing area and weighing. The most toxic tannery area identified was the weighing area (p <0.001), showing the lowest bioluminescence for both the solid (0.38 +/- 2.21) and liquid phases (0.01 +/- 0.001). Chromium was the metal present in the highest concentration indicating levels higher than the stipulated regulatory requirement of 0.5 mg Cr/m3 for total Cr (highest Cr concentration was at chemical handling at 209.24 mg l(-1)) in all dust samples. The weighing area had the highest Ni concentration (1.87 mg l(-1)) and the chemical handling area showed the highest Zn concentration (31.9 mg l(-1)). These results raise environmental health concerns, as occupational exposure to dust samples from this site has been shown to give rise to elevated concentrations (above the stipulated levels) of chromium in blood, urine and some body tissues, with inhalation being the main route. Health and Safety Executive (HSE), UK, and American Conference of Governmental Industrial Hygienist (ACGIH) and National Institute for Occupational Safety and Health (NIOSH), USA stipulates an occupational exposure limit of 0.5 mg Cr/m3 (8 h TWA) for total chromium. However, schedule 1 of Controls of substances hazardous to health (COSHH) regulations developed by HSE, indicate 0.05 mg m3 (8 h TWA reference periods) to be the limit for Cr (VI) exposure. The exposure limit for individual (e.g., Cr, Zn, Ni etc.) contaminants (homogeneity) was not exceeded, but potential impact of heterogeneity (multi-element synergistic effect) on toxicity requires application of the precautionary principle.

Altered porphyrin excretion and histopathology of greylag geese (Anser anser) exposed to soil contaminated with lead and arsenic in the Guadalquivir Marshes, southwestern Spain

Greylag geese (Anser anser) in the Guadalquivir Marshes (southwestern Spain) can be exposed to sources of inorganic pollution such as heavy metals and arsenic from mining activities or Pb shot used for hunting. We have sampled 270 fecal excreta in different areas of the marshes in 2001 to 2002 to evaluate the exposure to Pb, Zn, Cu, Mn, and As and to determine its relationship with soil ingestion and with the excretion of porphyrins and biliverdin as biomarkers. These effects and the histopathology of liver, kidney, and pancreas were also studied in 50 geese shot in 2002 to 2004. None of the geese had ingested Pb shot in the gizzard. This contrasts with earlier samplings before the ban of Pb shot for waterfowl hunting in 2001 and the removal of Pb shot in points of the Doñana National Park (Spain) in 1999 to 2000. The highest exposure through direct soil ingestion to Pb and other studied elements was observed in samples from Entremuros, the area of the Doñana Natural Park affected by the Aznalcóllar mine spill in 1998. Birds from Entremuros also more frequently showed mononuclear infiltrates in liver and kidney than birds from the unaffected areas, although other more specific lesions of Pb or Zn poisoning were not observed. The excretion of coproporphyrins, especially of the isomer I, was positively related to the fecal As concentration, and the ratio of coproporphyrin III/I was positively related to fecal Pb concentration. Biliary protoporphyrin IX concentration was also slightly related to hepatic Pb concentration. This study reflects biological effects on terrestrial animals by the mining pollution in Doñana that can be monitored with the simple noninvasive sampling of feces.

An ecotoxicological approach to assessing the impact of tanning industry effluent on river health

A study was conducted to investigate the sediment health and water quality of the River Sagana, Kenya, as impacted by the local tanning industry. Chemical analysis identified the main chemical pollutants (pentachlorophenols and chromium) while a bioassay addressed pollutant bioavailability. The bioassay, exploiting the luminescence response of a lux marked bacterial biosensor, was coupled to a dehydrogenase and Dapnia magna test to determine toxicity effects on sediments. Results highlighted the toxicity of the tannery effluent to the sediments at the point of discharge (64% of control bioluminescence) with gradual improvement downstream. There was a significant increase in dehydrogenase downstream, with the enzyme activity attaining a peak at 600 m, also indicating a gradual reduction of toxicity. Biological oxygen demand (19.56 mg L(-1)) dissolved oxygen (3.97 mg L(-1)) and high lethal dose value (85%) of D. magna also confirmed an initial stress at the point of discharge and recovery downstream. Optical density of surface water demonstrated an increase in suspended particulates and colour after the discharge point, eventually decreasing beyond 400 m. In conclusion, the study highlighted the importance of understanding the biogeochemistry of river systems impacted by industries discharging effluent into them and the invaluable role of a biosensor-based ecotoxicological approach to address effluent hazards, particularly in relation to river sediments.

Assessing the occupational risk of dust particles in the Kenyan tanning industry using rapid image processing and microscopy techniques

The purpose of this study was to investigate the occupational hazards within the tanning industry caused by contaminated dust. A qualitative assessment of the risk of human exposure to dust was made throughout a commercial Kenyan tannery. Using this information, high-risk points in the processing line were identified and dust sampling regimes developed. An optical set-up using microscopy and digital imaging techniques was used to determine dust particle numbers and size distributions. The results showed that chemical handling was the most hazardous (12 mg m(-3)). A Monte Carlo method was used to estimate the concentration of the dust in the air throughout the tannery during an 8 h working day. This showed that the high-risk area of the tannery was associated with mean concentrations of dust greater than the UK Statutory Instrument 2002 No. 2677. stipulated limits (exceeding 10 mg m(-3) (Inhalable dust limits) and 4 mg m(-3) (Respirable dust limits). This therefore has implications in terms of provision of personal protective equipment (PPE) to the tannery workers for the mitigation of occupational risk.

Flux and turnover of fixed carbon in soil microbial biomass of limed and unlimed plots of an upland grassland ecosystem

The influence of liming on rhizosphere microbial biomass C and incorporation of root exudates was studied in the field by in situ pulse labelling of temperate grassland vegetation with (13)CO(2) for a 3-day period. In plots that had been limed (CaCO(3) amended) annually for 3 years, incorporation into shoots and roots was, respectively, greater and lower than in unlimed plots. Analysis of chloroform-labile C demonstrated lower levels of (13)C incorporation into microbial biomass in limed soils compared to unlimed soils. The turnover of the recently assimilated (13)C compounds was faster in microbial biomass from limed than that from unlimed soils, suggesting that liming increases incorporation by microbial communities of root exudates. An exponential decay model of (13)C in total microbial biomass in limed soils indicated that the half-life of the tracer within this carbon pool was 4.7 days. Results are presented and discussed in relation to the absolute values of (13)C fixed and allocated within the plant-soil system.

Direct evidence showing the effect of root surface iron plaque on arsenite and arsenate uptake into rice (Oryza sativa) roots

The present study aimed to investigate the effects of root surface iron plaque on the uptake kinetics of arsenite and arsenate by excised roots of rice (Oryza sativa) seedlings. The results demonstrated that the presence of iron plaque enhanced arsenite and decreased arsenate uptake. Arsenite and arsenate uptake kinetics were adequately fitted by the Michaelis-Menten function in the absence of plaque, but produced poor fits to this function in the presence of plaque. Phosphate in the uptake solution did not have a significant effect on arsenite uptake irrespective of the presence of iron plaque; however phosphate had a significant effect on arsenate uptake. Without iron plaque, phosphate inhibited arsenate uptake. The presence of iron plaque diminished the effect of phosphate on arsenate uptake, possibly through a combined effect of arsenate desorption from iron plaque.

Isotopic identification of the sources of lead contamination for white storks (Ciconia ciconia) in a marshland ecosystem (Doñana, S.W. Spain)

White storks (Ciconia ciconia) fed in contaminated waters resulting from the Aznacollar acid mining-sludge spillage into the R. Guadiamar, which feeds the eastern flank of the Guadalquivir marshes (Doñana), S.W. Spain. The sludge was rich in a range of toxic elements, and in organic pollutants such as the aromatic amines. Storks did not exhibit elevated metals in their blood immediately following the accident, but chick blood collected the year following the accident showed genotoxic damage compared to the controls. In this study lead isotope analysis was used to assess if the storks had ingested sludge-derived contaminants. The sludge lead isotope ratio was distinct from that of the Doñana sediments. The stork blood lead isotope ratios exactly matched that of the sludge. It was concluded that the storks had ingested sludge-derived contaminants. A detailed study of the lead contamination along the R. Guadiamar and the R. Guadalquivir (of which the Guadiamar is a tributary) was also conducted to place the white stork colony lead exposure in the context of the spatial contamination of the storks' habitat.

Antimony bioavailability in mine soils

Five British former mining and smelting sites were investigated and found to have levels of total Sb of up to 700 mg kg(-1), indicating high levels of contamination which could be potentially harmful. However, this level of Sb was found to be biologically unavailable over a wide range of pH values, indicating that Sb is relatively unreactive and immobile in the surface layers of the soil, remaining where it is deposited rather than leaching into lower horizons and contaminating ground water. Sb, sparingly soluble in water, was unavailable to the bacterial biosensors tested. The bioluminescence responses were correlated to levels of co-contaminants such as arsenic and copper, rather than to Sb concentrations. This suggests that soil contamination by Sb due to mining and smelting operations is not a severe risk to the environment or human health provided that it is present as immobile species and contaminated sites are not used for purposes which increase the threat of exposure to identified receptors. Co-contaminants such as arsenic and copper are more bioavailable and may therefore be seen as a more significant risk.

A tripartite microbial reporter gene system for real-time assays of soil nutrient status

Plant-derived carbon is the substrate which drives the rate of microbial assimilation and turnover of nutrients, in particular N and P, within the rhizosphere. To develop a better understanding of rhizosphere dynamics, a tripartite reporter gene system has been developed. We used three lux-marked Pseudomonas fluorescens strains to report on soil (1) assimilable carbon, (2) N-status, and (3) P-status. In vivo studies using soil water, spiked with C, N and P to simulate rhizosphere conditions, showed that the tripartite reporter system can provide real-time assessment of carbon and nutrient status. Good quantitative agreement for bioluminescence output between reference material and soil water samples was found for the C and P reporters. With regard to soil nitrate, the minimum bioavailable concentration was found to be greater than that analytically detectable in soil water. This is the first time that bioavailable soil C, N and P have been quantified using a tripartite reporter gene system.

Arsenic accumulation and metabolism in rice (Oryza sativa L.)

The use of arsenic (As) contaminated groundwater for irrigation of crops has resulted in elevated concentrations of arsenic in agricultural soils in Bangladesh, West Bengal (India), and elsewhere. Paddy rice (Oryza sativa L.) is the main agricultural crop grown in the arsenic-affected areas of Bangladesh. There is, therefore, concern regarding accumulation of arsenic in rice grown those soils. A greenhouse study was conducted to examine the effects of arsenic-contaminated irrigation water on the growth of rice and uptake and speciation of arsenic. Treatments of the greenhouse experiment consisted of two phosphate doses and seven different arsenate concentrations ranging from 0 to 8 mg of As L(-1) applied regularly throughout the 170-day post-transplantation growing period until plants were ready for harvesting. Increasing the concentration of arsenate in irrigation water significantly decreased plant height, grain yield, the number of filled grains, grain weight, and root biomass, while the arsenic concentrations in root, straw, and rice husk increased significantly. Concentrations of arsenic in rice grain did not exceed the food hygiene concentration limit (1.0 mg of As kg(-1) dry weight). The concentrations of arsenic in rice straw (up to 91.8 mg kg(-1) for the highest As treatment) were of the same order of magnitude as root arsenic concentrations (up to 107.5 mg kg(-1)), suggesting that arsenic can be readily translocated to the shoot. While not covered by food hygiene regulations, rice straw is used as cattle feed in many countries including Bangladesh. The high arsenic concentrations may have the potential for adverse health effects on the cattle and an increase of arsenic exposure in humans via the plant-animal-human pathway. Arsenic concentrations in rice plant parts except husk were not affected by application of phosphate. As the concentration of arsenic in the rice grain was low, arsenic speciation was performed only on rice straw to predict the risk associated with feeding contaminated straw to the cattle. Speciation of arsenic in tissues (using HPLC-ICP-MS) revealed that the predominant species present in straw was arsenate followed by arsenite and dimethylarsinic acid (DMAA). As DMAA is only present at low concentrations, it is unlikely this will greatly alter the toxicity of arsenic present in rice.

Assessment of bioavailable arsenic and copper in soils and sediments from the Antofagasta region of northern Chile

Copper levels of nearly 500 mg l(-1) were measured in aqueous extracts of soil and sediment samples from the lowlands of Antofagasta. Arsenic levels of up to 183 mg l(-1) were found in river sediments, and 27.5 mg l(-1) arsenic was found at the location of a dam where potable water is extracted. This indicates that the arsenic contamination of water supplies reported recently for the pre-Andes may be a widespread problem throughout the region. Copper contamination from smelting activities also provides cause for concern as elevated levels were found in aqueous extracts of soil up to 20 km away from a smelter. This study went beyond traditional chemical analysis by assessing the potential benefits of using microbial biosensors as an alternative to determination of chemical speciation, to provide an environmentally relevant interpretation of soil/sediment residue levels. This approach is simple to use and enables a rapid, low cost assessment of pollutant bioavailability. It may, therefore, be of use for further investigations in the region and beyond.

Cities as Organisms

Since the UN report by the Brundtland Committee, sustainability in the built environment has mainly been seen from a technical focus on single buildings or products. With the energy efficiency approaching 100%, fossil resources depleting and a considerable part of the world still in need of better prosperity, the playing field of a technical focus has become very limited. It will most probably not lead to the sustainable development needed to avoid irreversible effects on climate, energy provision and, not least, society.
Cities are complex structures of independently functioning elements, all of which are nevertheless connected to different forms of infrastructure, which provide the necessary sources or solve the release of waste material. With the current ambitions regarding carbon- or energy-neutrality, retreating again to the scale of a building is likely to fail. Within an urban context a single building cannot become fully resource-independent, and need not, from our viewpoint. Cities should be considered as an organism that has the ability to intelligently exchange sources and waste flows. Especially in terms of energy, it can be made clear that the present situation in most cities are undesired: there is simultaneous demand for heat and cold, and in summer a lot of excess energy is lost, which needs to be produced again in winter. The solution for this is a system that intelligently exchanges and stores essential sources, e.g. energy, and that optimally utilises waste flows.
This new approach will be discussed and exemplified. The Rotterdam Energy Approach and Planning (REAP) will be illustrated as a means for urban planning, whereas Swarm Planning will be introduced as another nature-based principle for swift changes towards sustainability